Nitrileoxide compound

ABSTRACT

The present invention provides a compound of the formula (I): 
     
       
         
         
             
             
         
       
     
     wherein, R 1  is a hydrogen atom or a hydrocarbon group; R 2  is —R 4 —R 5 ; R 3  is —R 4 —R 5  or —R 4 —R 6 ; R 4  is a divalent organic group; R 5  is OH, SH, COOH or NHR 9 ; R 9  is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and R 6  is a hydrogen atom or an alkyl group having 1-6 carbon atoms.

TECHNICAL FIELD

The present invention relates to a nitrileoxide compound, and a polymercomprising the nitrileoxide compound.

BACKGROUND ART

A compound having a nitrileoxide group is known to be useful as areaction agent in various applications since it readily click-reactswith an unsaturated bond in other compound ([2+3] cycloadditionreaction).

With respect to the known nitrileoxide compound, Patent Literature 1discloses an aromatic nitrileoxide compound and Patent Literature 2discloses an aliphatic nitrileoxide compound, as a compound having lowmolecular weight. Patent Literature 3 discloses an acrylate orstyrene-based polymer having a nitrileoxide group as a compound havinghigh molecular weight.

On the other hand, a polymeric material is an important compound used ina wide range of applications. In particular, a fluorine-containingpolymeric material is widely used as an electronic member or a member ofa semiconductor manufacturing process equipment. As the means for curingthe polymeric material, usually a crosslinking agent (or a curing agent)has been used.

PRIOR ART LITERATURE Patent Literature

Patent Literature 1: Japanese Patent Application No. 2010-37289

Patent Literature 2: International Publication No. 2014/136952

Patent Literature 3: Japanese Patent Application No. 2013-112741

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

The polymeric material may contain a crosslinking agent unreacted as animpurity when the polymeric material is cured with a conventionalcrosslinking agent. The conventional crosslinking agent has a lowmolecular weight. When the polymeric material containing such impurityis used as a member of a semiconductor manufacturing process equipment,outgases are generated, thereby causing problems such as process errors.

Therefore, the object of the present invention is to provide a polymericmaterial which contains a small amount of low molecular weightimpurities when is cured.

Means to Solve the Problem

As a result of intensively studying of the inventors of the presentinvention in order to solve the above problem, the inventors have foundthat the problem can be solved by using a self-crosslinking polymercapable of crosslinking without using the crosslinking agent. Theinventors of the present invention have focused a nitrileoxide compoundcausing a click reaction, and have studied a polymer having anitrileoxide group. The inventors of the present invention have foundthat a polymer which is able to cause an intermolecular crosslinkingreaction and cure without the need of the conventional crosslinkingagent by introducing a plurality of nitrileoxide groups into themolecule of the polymer. In addition, the inventors have found that thepolymer having a plurality of nitrileoxide groups in the molecule can beused in place of the conventional crosslinking agent. It is noted thatthe known polymer having a nitrileoxide group is only a polymer havingone nitrileoxide group at the terminal of the acrylate or styrene-basedbackbone, and since such polymer has only one nitrileoxide group, itcannot crosslink between molecules.

Further, the inventors have also studied a process for producing thepolymer having a plurality of nitrileoxide groups. As a result, theinventors have focused a method of synthesizing a polymer by using amonomer having a nitrileoxide group, and have found that by reacting anitrileoxide monomer having two nucleophilic groups at the molecularterminals as the monomer with a condensation polymerizable or additionpolymerizable monomer, the polymer described above can successfully beobtained. In addition, the inventors have found that by performing thepolymerization using a compound having a nitrileoxide group and anethylenic double bond as a monomer, the polymer described above cansuccessfully be obtained.

Furthermore, the inventors have found that the polymer described inPatent Literature 3 is synthesized by performing the polymerizationproviding a the acrylate or styrene based main chain and using acompound having a nitrileoxide group as a terminator, and the reactionof functionalizing a terminal described in Patent Literature 3 is lowefficient. In addition, in this method, it is impossible to introducinga nitrileoxide group into a position other than the terminal of amolecular main chain of a polymer, for example, in central portion, andit is difficult to introducing a nitrileoxide group into both terminalsof the molecular main chain.

As a result of intensively studying of the inventors of the presentinvention with respect to the above problems, the inventors have foundthat by using a nitrileoxide compound having a nucleophilic group as apolymerization initiator, a nitrileoxide group may efficiently beintroduced into the polymer. In addition, the inventors have found thatby using this method, it is possible to introduce a nitrileoxide groupinto the central portion of a molecular main chain of a polymer and tointroduce a nitrileoxide group into the both terminals of the polymer.

Therefore, the present invention provides:

(1) A compound of the formula (I):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² is —R⁴—R⁵;

R³ is —R⁴—R⁵ or —R⁴—R⁶;

R⁴ is a divalent organic group;

R⁵ is each independently OH, SH, COOH or NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms;

(2) The compound according to the above (1) wherein R² and R³ are eachindependently —R⁴—R⁵;(3) The compound according to the above (1) wherein R² is —R⁴—R⁵, and R³is —R⁴—R⁵;(4) The compound according to any one of the above (1)-(3) wherein R⁴ is—R¹¹—R¹²—,

R¹¹ is an arylene having 3-10 carbon atoms or —CR⁷R⁸—,

R⁷ and R⁸ are each independently an alkyl group having 1-6 carbon atoms,and

R¹² is, a single bond, a linker having 1-10 atoms of the main chain;

(5) The compound according to any one of the above (1)-(4) wherein R¹ isan alkyl group having 1-16 carbon atoms, a cycloalkyl group having 3-20carbon atoms, an aryl group having 3-20 carbon atoms, or a(poly)alkylether group, which may be substituted by one or moresubstituents;(6) The compound according to any one of the above (1)-(5) wherein R⁵ isOH;(7) A compound of the formula (III):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group;

(8) The compound according to the above (7) wherein R²³ is —R²⁴—R²⁵—R²⁶

R²⁴ is a single bond, an alkylene having 1-6 carbon atoms, —CO—, —CO—O—,or —CO—NR— (wherein R is a hydrogen atom or an alkyl group);

R²⁵ is a linker having 1-20 atoms of the main chain;

R²⁶ is a single bond, an alkylene having 1-6 carbon atoms or —CR²⁷R²⁸—;and

R²⁷ and R²⁸ are each independently a hydrogen atom, an alkyl grouphaving 1-6 carbon atoms or an aryl group having 5-10 carbon atoms;

(9) The compound according of the above (8) wherein R²⁴ is —CO— or—CO—O—;

R²⁵ is a linker having 1-20 atoms of the main chain;

R²⁶ is —CR²⁷R²⁸—;

R²⁷ is an aryl group having 5-10 carbon atoms; and

R²⁸ is a hydrogen atom or an alkyl group having 1-6 carbon atoms;

(10) A copolymer comprising one or more monomer units of the formula(Ia):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) and R^(3′) are each independently —R⁴—R^(5′)—;

R⁴ is a divalent organic group;

R^(5′) is each independently —O—, —S—, —CO— or —NR⁹—; and

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms,

and one or more condensation polymerizable or addition polymerizablemonomer units;(11) A process of producing the copolymer according to the above (10),comprising a step of polymerizing one or more monomers of the formula(Ia′):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² and R³ are each independently, —R⁴—R⁵;

R⁴ is a divalent organic group;

R⁵ is each independently OH, SH, COOH or NHR⁹; and

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms

with one or more condensation polymerizable or addition polymerizablemonomers;(12) A polymer comprising one or more monomer units of the formula(IIa):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group;

(13) A polymer comprising one or more monomer units of the formula(IIIa):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group;

(14) A process of producing the copolymer according to the above (13),comprising a step of polymerizing one or more monomers of the formula(III):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group;

(15) A process of producing the copolymer according to the above (12),comprising a step of converting the CH₂NO₂ group of the polymeraccording to the above (13) to a CN⁺O⁻ group by dehydration;(16) A composition applied to a material containing a group reactivewith a nitrileoxide group, comprising one or more polymers according tothe above (10) or (12);(17) The composition according to the above (16), which is acrosslinking agent;(18) A polymer comprising one or more ring-opening polymerizable monomerunits, having a group of the formula (Ib):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) is —R⁴—R^(5′)

R³ is —R⁴—R⁶;

R⁴ is a divalent organic group;

R^(5′) is —O—, —S—, —CO—O— or —NR⁹—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms,

at one terminal of the main chain;(19) A polymer comprising one or more ring-opening polymerizable monomerunits, having a group of the formula (Ib):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) is —R⁴—R^(5′—;)

R³ is —R⁴—R⁶;

R⁴ is a divalent organic group;

R^(5′) is —O—, —S—, —CO—O— or —NR⁹—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms,

at one terminal of the main chain and a nitrileoxide group at the otherterminal of the main chain;(20) A polymer comprising one or more ring-opening polymerizable monomerunits, having one moiety of the formula (Ic):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) and R³ are each independently —R⁴—R^(5′)—;

R⁴ is a divalent organic group;

R⁵ is —O—, —S—, —CO— or —NR⁹—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R^(2′) and R^(3′) are directly attached to the polymerizable monomerunit,

in the molecular main chain;(21) A process of producing the copolymer according to any one of theabove (18)-(20), comprising a step of polymerizing one or morering-opening polymerizable monomer by using a compound of the formula(Id′) as an polymerization initiator:

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² is −R⁴—R⁵;

R³ is —R⁴—R⁵ or —R⁴—R⁶;

R⁴ is a divalent organic group;

R⁵ is OH, SH, —COOH or —NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms;

(22) A composition applied to a material containing a group reactivewith a nitrileoxide group, comprising one or more polymers according toany one of the above (18)-(20);(23) The composition according to the above (22), which is a graftingagent;(24) The composition according to the above (22), which is acrosslinking agent.

Effect of the Invention

According to the present invention, the polymer compound having aplurality of nitrileoxide groups is provided. Since such polymercompound has a plurality of nitrileoxide groups, the polymer functionsas a crosslinking agent itself, and can self-crosslink and cure withoutusing a conventional crosslinking agent having low molecular weight. Inaddition, the polymer compound of the present invention can be used as acrosslinking agent in place of conventional crosslinking agent havinglow molecular weight. Since the polymer compound of the presentinvention has high molecular weight, the polymer compound hard to becomeoutgases or effluent component, and even when the polymer compound isused as a member of a semiconductor manufacturing process apparatus, thepolymer compound hard to cause process errors. According to the presentinvention, a nitrileoxide group is able to be introduced into anyposition such as one terminal, both terminals, or a central portion ofthe polymer compound.

EMBODIMENTS TO CARRY OUT THE INVENTION

In the present specification, unless otherwise specified, “a hydrocarbongroup” means a group containing a carbon atom and a hydrogen atom(provided that, a part of or all of hydrogen atoms may be replaced withthe following substituents). Examples of the hydrocarbon group include,but are not particularly limited to, for example, an aliphatichydrocarbon group, an aromatic hydrocarbon group, and the like, whichmay be substituted by one or more substituents, a hydrocarbon grouphaving 1-20 carbon atoms. It is noted that the hydrocarbon group mayhave one or more N, O, S, or the like at its end or in its molecularchain.

In the present specification, unless otherwise specified, the “aliphatichydrocarbon group” may be straight, branched or cyclic and saturated orunsaturated, and may contain one or more rings. Examples of the“aliphatic hydrocarbon group” include, but are not particularly limitedto, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkylgroup, a cycloalkenyl group. The “aliphatic hydrocarbon group” may besubstituted by one or more substituents.

In the present specification, unless otherwise specified, the “alkylgroup” may be straight or branched, and is for example an alkyl grouphaving 1-20, preferably 1-12, more preferably 1-6 carbon atoms. Examplesof the “alkyl group” include, but are not particularly limited to, amethyl group, an ethyl group, a propyl group, an isopropyl group, ann-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group,a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, an n-hexylgroup, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentylgroup, a 4-methylpentyl group, an n-hexyl group, a 2-methylpentyl group,a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a2-ethylbutyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutylgroup, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, a1-ethyl-1-methylpropyl group, a 1-ethyl-2-methylpropyl group, and thelike. The “alkyl group” may be substituted by one or more substituents.

In the present specification, unless otherwise specified, the “alkenylgroup” may be straight or branched, and is for example an alkenyl grouphaving 2-20, preferably 2-12, more preferably 2-6 carbon atoms. Examplesof the “alkenyl group” include, but are not particularly limited to, forexample, a group which at least one carbon-carbon single bond in theabove alkyl group is replaced with a carbon-carbon double bond,specifically, a vinyl group, an allyl group, a 1-propenyl group, anisopropenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenylgroup, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1-pentenyl group, a 1-hexenyl group, a 1,3-hexadienyl group, a1,5-hexadienyl group, and the like. The “alkenyl group” may besubstituted by one or more substituents.

In the present specification, unless otherwise specified, the “alkynylgroup” may be straight or branched, and is for example an alkynyl grouphaving 2-20, preferably 2-12, more preferably 2-6 carbon atoms. Examplesof the “alkynyl group” include, but are not particularly limited to, forexample, a group which at least one carbon-carbon single bond in theabove alkyl group is replaced with a carbon-carbon triple bond,specifically, an ethynyl group, a 1-propynyl group, a 2-propynyl group,a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a1-methyl-2-propynyl group, a 1-pentynyl group, a 1-ethyl-2-propynylgroup, a 1-hexynyl group, a 2-hexynyl group, and the like. The “alkynylgroup” may be substituted by one or more substituents.

In the present specification, unless otherwise specified, the“cycloalkyl group” is a cyclic alkyl group having 3-20, preferably 5-12carbon atoms. Examples of the “cycloalkyl group” include, but are notparticularly limited to, for example, a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, acyclooctyl group, and the like. The “cycloalkyl group” may besubstituted by one or more substituents.

In the present specification, unless otherwise specified, the“cycloalkenyl group” is a cyclic alkenyl group having 3-20, preferably5-12 carbon atoms. Examples of the “cycloalkenyl group” include, but arenot particularly limited to, for example, a cyclopropenyl group, acyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, acycloheptenyl group, a cyclooctenyl group, and the like. The“cycloalkenyl group” may be substituted by one or more substituents.

In the present specification, unless otherwise specified, the “aromatichydrocarbon group (hereinafter, referred to as an aryl group)” may bemonocyclic or polycyclic, for example bicyclic or tricyclic, or may bean aromatic heterocyclic group (hereinafter, referred to as a heteroarylgroup). Examples of the “aromatic hydrocarbon group” include, but arenot particularly limited to, an aryl group having 3-20 carbon atoms suchas a phenyl group, a naphthyl group, and a heteroaryl group having 3-20carbon atoms such as a furyl group, a thienyl group, a pyridyl group, anindolyl group, a quinolyl group, an isoquinolyl group, or an imidazolylgroup. The “aromatic hydrocarbon group” may be substituted by one ormore substituents.

In the present specification, unless otherwise specified, the “alkylenegroup” is a divalent group obtained by removing a hydrogen atom on acarbon atom in the alkyl group described above.

In the present specification, unless otherwise specified, the“(poly)alkylether group” is a group obtained by inserting an ethericoxygen atom into one or more carbon-carbon bonds in the alkyl groupdescribed above

A preferable (poly)alkylether group is a group of the following formula:

R—(O(CH₂)_(n))_(m)—

wherein R is a C₁₋₁₆ alkyl group, m is an integer of 1-300, and n is ateach occurrence an integer of 1-6.

Another preferable (poly)alkylether group is a group of the followingformula:

R—(OC₄H₈)_(a)—(OC₃H₆)_(b)—(OC₂H₄)_(c)—(OCH₂)_(d)—

wherein:

R is a C₁₋₁₆ alkyl group;

a, b, c and d are each independently an integer of 0 or more and 200 orless, the sum of a, b, c and d is at least one, and the occurrence orderof the respective repeating units in parentheses with the subscript a,b, c or d is not limited in the formula.

When the (poly)alkylether group described above is used as a divalentgroup, it is a group of the following formula:

—R′—(OC₄H₈)_(a)—(OC₃H₆)_(b)—(OC₂H₄)_(c)—(OCH₂)_(d)—

wherein R′ is a C₀₋₁₆ alkylene group. It is noted that in the presentspecification, C₀ means that a carbon atom is absent, for example aC₀₋₁₆ alkylene group is a single bond or a C₁₋₁₆ alkylene group.

In the present specification, unless otherwise specified, thehydrocarbon group, the alkyl group, the alkenyl group, the alkynylgroup, the cycloalkyl group, the cycloalkenyl group, the aromatichydrocarbon group and an alkylene group may be substituted. Examples ofthe substituents include, but are not particularly limited to, forexample, an oxygen atom; a halogen atom (fluorine, chlorine, bromine,iodine); a hydroxyl group; an unsubstituted, mono-substituted ordi-substituted amino group; a nitro group; an azide group; a C₁₋₁₆ alkylgroup, a C₂₋₁₆ alkenyl group, a C₂₋₁₆ alkynyl group, a C₃₋₁₆ cycloalkylgroup, a C₃₋₁₆ cycloalkenyl group, a C₆₋₁₆ heterocycloalkyl group, aC₆₋₁₆ heterocycloalkenyl group, a C₆₋₁₆ aryl group, a C₆₋₁₆ heteroarylgroup, a C₁₋₁₆ alkoxy group, a C₆₋₁₆ aryloxy, a C₁₋₁₆ alkylthio or aC₁₋₂₀ (poly)alkyl ether group which may be substituted by one or morehalogen atoms; —O—C(O)—OR^(a), —O—C(O)—NR^(a) ₂, —C(O)—R^(a),—C(O)—OR^(a), —NR^(a)—C(O)—R^(a), —NR^(a)—C(NR^(a))—R^(a),—C(NR^(a))—R^(a) or —C(NR^(a))—NR^(a) ₂ (wherein R^(a) represents eachindependently a hydrogen atom, a C₁₋₁₆ alkyl group, a C₂₋₁₆ alkenylgroup, a C₂₋₁₆ alkynyl group, a C₃₋₁₆ cycloalkyl group, a C₃₋₁₆cycloalkenyl group, a C₁₋₁₆ heterocycloalkyl group, a C₁₋₁₆heterocycloalkenyl group, a C₁₋₁₆ aryl group or a C₆₋₁₆ heteroarylgroup)

The “mono-substituted amino group” represents an amino group substitutedby one substituent independently selected from the group consisting of aC₁₋₁₆ alkyl group, a C₂₋₁₆ alkenyl group, a C₂₋₁₆ alkynyl group, a C₃₋₁₆cycloalkyl group, a C₃₋₁₆ a cycloalkenyl group, a C₁₋₁₆ heterocycloalkylgroup, a C₁₋₁₆ heterocycloalkenyl group, a C₁₋₁₆ aryl group and a C₆₋₁₆heteroaryl group, but is not particularly limited thereto. Examples ofthe “mono-substituted amino group” include, but are not particularlylimited to, methylamino, ethylamino, phenylamino, and the like.

The “di-substituted amino group” represents an amino group substitutedby two substituents independently selected from the group consisting ofa C₁₋₁₆ alkyl group, a C₂₋₁₆ alkenyl group, a C₂₋₁₆ alkynyl group, aC₃₋₁₆ cycloalkyl group, a C₃₋₁₆ a cycloalkenyl group, a C₆₋₁₆heterocycloalkyl group, a C₆₋₁₆ heterocycloalkenyl group, a C₆₋₁₆ arylgroup and a C₆₋₁₆ heteroaryl group, but are not particularly limitedthereto. Examples of the “di-substituted amino group” include, but arenot particularly limited to, dimethylamino, diethylamino, diphenylamino,and the like.

Examples of the “C₁₋₁₆ alkoxy group” include, but are not particularlylimited to, for example, a methoxy group, an ethoxy group, an n-propoxygroup, an isopropoxy group, an n-butoxy group, an isobutoxy group, asec-butoxy group, a tert-butoxy group, an n-pentyloxy group, anisopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, a1-ethylpropoxy group, an n-hexyloxy group, an isohexyloxy group, aneohexyloxy group, a 2-ethylbutoxy group, and the like.

Examples of the “C₆₋₁₆ aryloxy” include, but are not particularlylimited to, for example, phenoxy, naphthyloxy, and the like.

Examples of the “C₁₋₁₆ alkylthio” include, but are not particularlylimited to, for example, methylthio, ethylthio, propylthio,isopropylthio, butylthio, sec-butylthio, tert-butylthio, and the like.

In the present specification, unless otherwise specified, the “halogen(or halogen atom)” means a fluorine atom, a chlorine atom, a bromineatom, an iodine atom, and the like.

In the present specification, unless otherwise specified, the“perfluoroalkyl group” means a group which all hydrogen atoms in theabove alkyl group are replaced with a fluorine atom, and is representedby —C_(m)F_(2m+1) wherein m is an integer, specifically an integer of1-16, for example an integer of 1-12 or 1-6. The “perfluoroalkyl group”may be straight or branched, preferably straight.

Hereinafter, the compound of the present invention will be describedbelow.

The present invention provides a compound of the formula (I):

In the formula (I), R¹ is a hydrogen atom or a hydrocarbon group,preferably a hydrocarbon group.

The hydrocarbon group in R¹ is an alkyl group having 1-16 carbon atoms,a cycloalkyl group having 3-20 carbon atoms, an aryl group having 3-20carbon atoms, or a (poly)alkylether group. These groups may have one ormore substituents. Examples of the substituents include, but are notlimited to, preferably a halogen atom (for example, fluorine, chlorine,bromine, iodine), an alkyl group having 1-10 carbon atoms, a cycloalkylgroup having 3-14 carbon atoms, an aryl group having 3-14 carbon atoms,or a (poly)alkylether group having 1-10 carbon atoms.

In one embodiment, R¹ is R^(1′)—Z—. In the formula, R^(1′) is ahydrocarbon group. In one embodiment, R^(1′) is an alkyl group having1-16 carbon atoms or (poly)alkylether, which may be substituted byfluorine. When they are substituted by fluorine, these alkyl groups or(poly)alkylether groups may be preferably a perfluoroalkyl group, aperfluoro(poly)alkylether group, perfluoroalkyl-(CH₂)_(n)—, orperfluoro(poly)alkylether-(CH₂)_(n)—. In another embodiment, R¹¹ may beH(CH₂)_(n), F(CF₂)_(m), CF(F(CF₂)_(m))₂—, H(CF₂)_(m)—,F(CF₂)_(m)—(OCF(CF₃)CF₂)_(p)—OCF(CF₃)—, or (F(CF₂)_(m))₂—C(CH₃)—CF₂—,wherein n is an integer of 1-6, m is an integer of 1-8, and p is aninteger of 0-4. In the formula, Z is a single bond or —(CH₂)₁O— wherein1 is an integer of 0-6.

In the formula (I), R² is —R⁴—R⁵.

In the formula (I), R³ is —R⁴—R⁵ or —R⁴—R⁶.

R⁴ is a divalent organic group. R⁴ is preferably, —R¹¹—R¹²—.

R¹¹ is cycloalkylene having 3-10 carbon atoms, an arylene having 3-10carbon atoms or —CR⁷R⁸—.

R⁷ and R⁸ are each independently a hydrogen atom or an alkyl grouphaving 1-6 carbon atoms. The alkyl group having 1-6 carbon atoms ispreferably an alkyl group having 1-3 carbon atoms, for example, a methylgroup, an ethyl group or a propyl group.

With respect to the hydrocarbon of —CR⁷R⁸— preferably has largersubstitution level. That is, preferably, at least one of R⁷ and R⁸ is analkyl group having 1-6 carbon atoms. When one of R⁷ and R⁸ is an alkylgroup having 1-6 carbon atoms, the carbon atom of —CR⁷R⁸— is a tertiarycarbon (however, a secondary carbon when R¹² is a single bond and R⁶ isa hydrogen atom), the stability of the nitrileoxide group is increased.When both of R⁷ and R⁸ are an alkyl group having 1-6 carbon atoms, acarbon atom of —CR⁷R⁸— is quaternary carbon (however, a tertiary carbonwhen R¹² is a single bond, and R⁶ is a hydrogen atom), the stability ofthe nitrileoxide group is more increased.

R¹¹ is preferably an arylene having 3-10 carbon atoms or —CR⁷R⁸— whereinR⁷ and R⁸ are an alkyl group having 1-6 carbon atoms, more preferably anarylene having 3-10 carbon atoms, for example, phenylene.

R¹² is a single bond or a linker having 1-10 atoms of the main chain.

The linker having 1-10 atoms of the main chain is, but not particularlylimited to, for example, an alkylene group, a cycloalkylene group, aheterocycloalkylene group, an arylene group, a heteroarylene group or adivalent (poly)alkylether group, or a combination thereof, andpreferably an alkylene group or a divalent (poly)alkylether group. Thesegroups may have one or more substituents. Examples of the substituentsinclude, but are not limited to, preferably a halogen atom (for example,fluorine, chlorine, bromine, iodine), an alkyl group having 1-10 carbonatoms, a cycloalkyl group having 3-14 carbon atoms, an aryl group having3-14 carbon atoms, or a (poly)alkylether group having 1-10 carbon atoms.

Preferable R⁴ is a phenylene group, phenylene-an alkylene group,phenylene-oxyalkylene group, or phenylene-polyalkylether group. In the—R⁴—R⁵ group, R⁴ is more preferably, phenylene-alkylene,phenylene-oxyalkylene group or phenylene-polyalkylether group

In one embodiment, the —R⁴—R⁶ group may be a phenyl group.

R⁵ is OH, SH, COOH or NHR⁹, preferably OH, SH, COOH or NH₂, morepreferably OH.

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms. Thealkyl group having 1-6 carbon atoms is preferably an alkyl group having1-3 carbon atoms, particularly a methyl group, an ethyl group or apropyl group, more preferably a methyl group. R⁹ is preferably ahydrogen atom.

Since —R⁴—R⁵ has R⁵ which is a reactive group at the terminal, acompound of the formula (I) can cause various reactions by this group.

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms. Thealkyl group having 1-6 carbon atoms is preferably an alkyl group having1-3 carbon atoms, particularly a methyl group, an ethyl group or apropyl group, more preferably a methyl group. R⁶ is preferably ahydrogen atom.

A preferable compound of the formula (I) is a compound wherein R¹ is analkyl group having 1-10 carbon atoms, R² and R³ are —R⁴—R⁵, R⁴ isphenylene, phenylene-alkylene, phenylene-oxyalkylene orphenylene-polyalkylether group, and R⁵ is OH.

A more preferable compound of the formula (I) is a compound wherein R¹is an alkyl group having 1-10 carbon atoms, R² and R³ are —R⁴—R⁶, R⁴ isa phenylene-oxyalkylene or phenylene-polyalkylether group, and R⁵ is OH.

Another preferable compound of the formula (I) is a compound wherein R¹is an alkyl group having 1-10 carbon atoms, R² is —R⁴—R⁵, R³ is —R⁴—R⁶,R⁴ is phenylene, phenylene-alkylene, phenylene-oxyalkylene orphenylene-polyalkylether group, and R⁵ is OH.

A more preferable compound of the formula (I) is a compound wherein R¹is an alkyl group having 1-10 carbon atoms, R² is —R⁴—R⁵ (wherein R⁴ isa phenylene-oxyalkylene or phenylene-polyalkylether group), R³ is —R⁴—R⁶(wherein R⁴ is phenylene, phenylene-alkylene, phenylene-oxyalkylene orphenylene-polyalkylether group), and R⁵ is OH.

Since the nitrileoxide compound of the formula (I) has two condensationpolymerizable or addition polymerizable groups (OH, SH, COOH or NHR⁹) inthe molecule, the nitrileoxide compound can be used as a raw monomer forcondensation polymerization or addition polymerization reaction.Therefore, the present invention provides a monomer of the formula(Ia′):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² and R³ are each independently —R⁴—R⁵;

R⁴ is a divalent organic group;

R⁵ is OH, SH, COOH or NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms.

Since the nitrileoxide compound of the formula (I) has a nucleophilicgroup (OH, SH, COOH or NHR⁹), the nitrileoxide compound can be used asan initiator in a ring-opening polymerization reaction. Therefore, thepresent invention provides an initiator of the formula (Id′):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² is —R⁴—R⁵;

R³ is —R⁴—R⁵ or —R⁴—R⁶;

R⁴ is a divalent organic group;

R⁵ is OH, SH, COOH or NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms.

The present invention provides a compound of the formula (III):

In the formula (III), R²¹ and R²² are a hydrogen atom or an alkyl group.The alkyl group is, but not particularly limited to, preferably an alkylgroup having 1-6 carbon atoms, more preferably an alkyl group having 1-3carbon atoms, further preferably a methyl group. R²¹ and R²² arepreferably a hydrogen atom or a methyl group, more preferably a hydrogenatom.

In the formula (III), R²³ is a divalent organic group.

In one embodiment, R²³ is —R²⁴—R²⁵—R²⁶—. It is noted that R²⁴ in thisgroup is attached to a carbon tom having an ethylenic double bond, andR²⁶ is attached to a nitrileoxide group.

R²⁴ is a single bond, an alkylene having 1-6 carbon atoms, —CO— or—CO—O—, —NR—CO— (R is a hydrogen atom or an alkyl group), —O—CO—,

R²⁵ is a linker having 1-20 atoms of the main chain,

R²⁶ is a single bond, an alkylene having 1-6 carbon atoms or —CR²⁷R²⁸—,

R²⁷ and R²⁸ are each independently a hydrogen atom, an alkyl grouphaving 1-6 carbon atoms or an aryl group having 5-10 carbon atoms.

In the compound of the formula (III), when R²⁷ is —CR²⁷R²⁸—, thenitrileoxide group is attached to this carbon atom. In order to increasethe stability of nitrileoxide, this carbon atom is preferably a tertiarycarbon, more preferably quaternary carbon.

In a preferable embodiment,

R²⁴ is —CO—, —CO—NR— (R is an alkyl group or a hydrogen atom) or —CO—O—,—NR—CO— (R is a hydrogen atom or an alkyl group), —O—CO—;

R²⁵ is a linker having 1-20 atoms of the main chain;

R²⁶ is —CR²⁷R²⁸—

R²⁷ is an aryl group having 5-10 carbon atoms; and

R²⁸ is a hydrogen atom or an alkyl group having 1-6 carbon atoms, morepreferably an alkyl group having 1-6 carbon atoms.

The linker having 1-20 atoms of the main chain of R²⁵ is, but notparticularly limited to, for example, a group or a combination of two ormore groups selected from the group consisting of an alkylene group, acycloalkylene group, an arylene group, a carbonyl group, an ester group(—COO— or —OCO—), an amide group (—CONH₂— or —NH₂CO—), —O— and —S—.These group may be substituted by one or more substituents, for examplesubstituent selected from the group consisting of a halogen atom (forexample, fluorine, chlorine, bromine or iodine, preferably fluorine), analkyl group having 1-6 carbon atoms, a cycloalkyl group having 3-10carbon atoms and an aryl group having 3-10 carbon atoms.

R²⁵ is preferably,

—(CH₂CH₂—O)_(p1)— (p1 is an integer of 1-6),

—(CHR³¹)_(p2)—O— (p2 is an integer of 1-9, and R³¹ is a hydrogen atom ora methyl group),

—(CH₂CH₂—O)_(p3)—CONH—CH₂CH₂—O— (p3 is an integer of 1-5),

—(CH₂CH₂)_(p4)—O—(CH₂CH₂)_(p5)— (p4 is an integer of 1-16, and p5 is aninteger of 1-16),

—(CH₂)_(p6)—O—CONH—(CH₂)_(p7)— (p6 is an integer of 1-8, and p7 is aninteger of 1-8),

—(CH₂)_(p8)— (p8 is an integer of 1-10),

-phenyl-, or

—O— (in this case, R¹ is not —O— and —CO—O—).

R²⁵ is more preferably

—(CH₂CH₂—O)_(p1)— (p1 is an integer of 1-6),

—(CHR³¹)_(p2)—O— (p2 is an integer of 1-9, and R³¹ is a hydrogen atom ora methyl group),

—(CH₂)_(p8)— (p8 is an integer of 1-10), or

-phenyl-.

The compound of the formula (III) has the —CH₂NO₂ group at the terminal.By subjecting this group to dehydration, this group can be converted tothe —C≡N⁺O⁻ group. By polymerizing the compound of the formula (III),and then dehydrating the —CH₂NO₂ group of the resulting polymer, apolymer having a plurality of nitrileoxide groups can be obtained.

The dehydration can be performed, but not particularly limited, by usinga concentrated sulfuric acid, trifluoromethanesulfonic acid,trifluoromethane sulfonimide, or phenyl isocyanate, or other strong acidhaving a non-nucleophilic counter anion.

In a preferable embodiment, the dehydration is performed by using anisocyanate compound in the presence of a base, particularly preferablyby using phenyl isocyanate in the presence of triethylamine.

The present invention provides a copolymer comprising one or moremonomer units of the formula (Ia):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) and R^(3′) are each independently, —R⁴—R^(5′)— wherein R⁴ isattached to a carbon atom having a nitrileoxide group;

R⁴ is a divalent organic group;

R^(5′) is each independently —O—, —S—, —CO— or —NR⁹—; and

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms,

and one or more condensation polymerizable or addition polymerizablemonomer units.

When the polymer consists of for example only one type of the monomerunit of the formula (Ia) and only one type of the condensationpolymerizable or addition polymerizable monomer unit, the polymer maycomprise a polymer of the following formula:

wherein R¹, R^(2′) and R^(3′) are as defined in the formula (Ia),

Mon is a condensation polymerizable or addition polymerizable monomerunit; and

n is any integer.

The copolymer can be obtained by condensation polymerizing or additionpolymerizing one or more compounds of the formula (I) (both of R² and R³are —R⁴—R⁵) and one or more condensation polymerizable or additionpolymerizable monomers. Therefore, the present invention provides aprocess for producing the copolymer comprising a monomer unit of theformula (Ia) and one or more condensation polymerizable or additionpolymerizable monomer units, comprising a step of polymerizing a monomerof the formula (Ia′):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² and R³ are each independently —R⁴—R⁵;

R⁴ is a divalent organic group;

R⁵ is OH, SH, COOH or NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms,

and one or more condensation polymerizable or addition polymerizablemonomers.

The monomer unit of the formula (Ia) corresponds to a monomer of theformula (I).

In the formula (Ia), R¹ is as defined for R¹ in the formula (I), and isa hydrogen atom or a hydrocarbon group.

In the formula (Ia), R^(2′) and R^(3′) are as defined for R² and R³ inthe formula (I), respectively, is a residue of R² and R³ aftercondensation polymerization or addition polymerization.

R^(2′) and R^(3′) are each independently —R⁴—R^(5′)—. R^(5′) correspondsto R⁵ in the formula (I), and is a divalent group in which a leavinggroup is removed from R⁵. R^(5′) is specifically each independently —O—,—S—, —CO— or —NR⁹—.

R⁹ is as defined for R⁹ in the formula (I), is a hydrogen atom or analkyl group having 1-6 carbon atoms.

In the copolymer, a structure of one or more condensation polymerizableor addition polymerizable monomer units is not limited, and may be aresidue of various condensation polymerizable or addition polymerizablemonomers.

The one or more condensation polymerizable monomers used in producing ofthe above copolymer is not limited as long as it is a compound havingtwo or more group polymerizable with R⁵ (for example, —COCl, —COBr,—COF, —OH, —F, —Cl, —Br, —I, —COOH, —NH₂, carboxylic acid anhydride,etc., depending on the type of R⁵)

Examples of the condensation polymerizable monomer include, but are notparticularly limited, as follows:

Hal-CO—R⁴¹—CO-Hal

wherein: Hal is a halogen atom, preferably chlorine, bromine, fluorine,particularly preferably chlorine,

R⁴¹ is an alkyl group or an aryl group;

Fluoroarenes (for example, hexafluorobenzene,bis(4-fluorophenyl)ketone),

Chloroarenes (for example, dichlorobenzene, bis(4-chlorophenyl)ketone),

Aliphatic chloride (for example, dichloromethane, 1,2-dichloroethane,bifunctional benzyl chloride),

Aliphatic bromide (for example, dibromomethane, bifunctional benzylbromide, α,ω-dibromide oligomethylene),

Aliphatic iodide (for example, diiodomethane),

Aromatic tetra acid anhydride,

Aromatic diamine,

Aromatic hydroxy amine

The one or more addition polymerizable monomers used in producing of theabove copolymer is not limited as long as the compound comprises two ormore groups to which R⁵ can added (for example, an epoxy group, —C═O,—C═C—, —C≡N, —N═C═O, —N═C═S, carbodiimide, ketene, keteneimine, or thelike).

Examples of the addition polymerizable monomer include, but are notparticularly limited, as follows:

EPO-CH₂—R⁴²—CH₂-EPO;

H—C(O)—R⁴²—C(O)H;

N≡C—R⁴²—C≡N;

O═C═N—R⁴²—N═C═O;

S═C═N—R⁴²—N═C═S

wherein: EPO is an epoxy group, and

R⁴² is an alkylene group, an arylene group or a divalent group whichthese groups are linked, which may be substituted by a fluorine atom,for example a perfluoroalkylene group.

In one embodiment, in producing of the copolymer, further condensationpolymerizable or addition polymerizable monomer may be used. The furthercondensation polymerizable or addition polymerizable monomer may be thatcapable of condensation or addition reaction with a compound having oneor more groups which are not directly reacted with the compound of theformula (I) and are able to condensation polymerize or additionpolymerize with R⁵. For example, example of the monomer may be acompound having two same groups as R⁵ in the compound of the formula (I)and does not fall in the scope of the formula (I).

Examples of the further condensation polymerizable monomer include agroup of the formula:

wherein R¹, R² and R³ are as defined for R¹, R² and R³ in the formula(I), and

R⁵¹ is an alkyl group or an aryl group.

In one embodiment, the polymer may be a polymer obtained by carbonmonoxide insertion reaction. In this case, —CO— group exists between themonomer unit of the formula (Ia) and the condensation polymerizable oraddition polymerizable monomer unit.

The polymer described above may include, for example, when the polymerconsists of only one monomer unit of the formula (Ia) and only onecondensation polymerizable monomer unit or addition polymerizablemonomer, a polymer of the following formula:

wherein R¹, R^(2′) and R^(3′) are as defined in the formula (Ia),

Mon is a condensation polymerizable monomer unit or additionpolymerizable monomer unit; and

n is any integer.

In the above embodiment, the polymerizable monomer unit may be a monomerunit of the formula (Ia′):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) and R^(3′) are each independently —R⁴— or —R⁴—R^(5′)— wherein R⁴is attached to a carbon atom having a nitrileoxide group;

R⁴ is a divalent organic group;

R^(5′) is each independently —O—, —S—, —CO— or —NR⁹—; and

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms. Themonomer unit of the formula (Ia′) and the monomer unit of the formula(Ia) are derived from the monomer of the same formula (I).

The above polymer may include a polymer of the following formula:

wherein R¹, R^(2′), R^(3′) and R⁴ are as defined in the formula (Ia),and

n is any integer.

The above polymer can be obtained by reacting the monomer of the formula(I), and optionally a condensation polymerizable monomer, and carbonmonoxide in the presence of a transition metal such as Pd. The reactioncan be represented by the following scheme, and known as a carbonmonoxide insertion reaction.

wherein X is a leaving group, and the other symbols are as definedabove.

wherein each symbol is as defined above.

Specifically, it includes the following reaction.

The present invention provides a homopolymer or copolymer comprising oneor more monomer units of the formula (IIIa):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group.

The above polymer can be obtained by polymerizing one or more compoundsof the formula (III). Therefore, the present invention provides aprocess for producing a polymer comprising one or more monomer units ofthe formula (IIIa), comprising a step of polymerizing a monomer of theformula (III):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group.

One or more compounds of the formula (III) describe above can bepolymerized with one or more polymerizable monomers. In this case, acopolymer comprising one or more monomer units of the formula (IIIa) andone or more polymerizable monomer units.

The monomer unit of the formula (IIIa) corresponds to the monomer of theformula (III).

In the formula (IIIa), R²¹ is as defined for R²¹ in the formula (III),and is a hydrogen atom or an alkyl group.

In the formula (IIIa), R²² is as defined for R²² in the formula (III),and is a hydrogen atom or an alkyl group.

In the formula (IIIa), R²³ is as defined for R²³ in the formula (III),and is a divalent organic group

The present invention provides a homopolymer or a copolymer comprisingone or more monomer units of the formula (IIa):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group.

The present invention provides a copolymer comprising one or moremonomer units of the formula (IIa) and one or more polymerizable monomerunit.

The polymer comprising the monomer unit of the formula (IIa) can beproduced by dehydrating a CH₂NO₂ group in the corresponding polymercomprising the monomer unit of the formula (IIIa) to convert a CN⁺O⁻group.

The structure of one or more polymerizable monomer unit in the abovecopolymer may be a residue of various monomers.

One or more polymerizable monomers used in producing of the abovepolymer are not particularly limited, and for example, a radicalpolymerizable monomer, an anion polymerizable monomer, a cationpolymerizable monomer, a coordination polymerizable monomer can be used.Preferable polymerizable monomer is a radical polymerizable monomer.

The present invention provides a polymer comprising a monomer unit ofthe formula (Xa) or the formula (Xb):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group.

The polymer of the formula (Xa) or the formula (Xb) can be obtained bydehydrating a compound of the formula (III):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group,

to obtain a monomer of the formula (II):

wherein:

R²¹ is a hydrogen atom or an alkyl group;

R²² is a hydrogen atom or an alkyl group; and

R²³ is a divalent organic group,

and polymerizing the monomer.

The present invention provides a polymer comprising one or morering-opening polymerizable monomer units, having a group of the formula(Ib):

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) is —R⁴—R^(5′)— wherein R⁴ is a carbon atom having a nitrileoxidegroup;

R³ is —R⁴—R⁶;

R⁴ is a divalent organic group;

R^(5′) is —O—, —S—, —CO—O— or —NR⁹—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms, at oneterminal.

The polymer described above, when for example it comprises only onepolymerizable monomer unit, can be represented by the following formula.

wherein R¹, R^(2′) and R³ are as defined in the formula (Ib),

Mon is a polymerizable monomer unit; and

n is any integer.

The polymer described above can be obtained by polymerizing one or morecompounds of the formula (I) wherein R² is —R⁴—R⁵, and R³ is —R⁴—R⁶, andone or more ring-opening polymerizable monomers. Therefore, the presentinvention provides a process for producing the polymer comprising one ormore ring-opening polymerizable monomer units wherein the polymer hasone group of the formula (Ib) at one terminal of the main chain,comprising a step of polymerizing one or more ring-opening polymerizablemonomer by using the formula (Ib′) as an initiator:

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² is —R⁴—R⁵;

R³ is —R⁴—R⁶;

R⁴ is a divalent organic group;

R⁵ is OH, —SH, —COOH or —NHR⁹;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms.

The present invention provides a polymer comprising one or morering-opening polymerizable monomer units wherein the polymer has a groupof the formula (Ib):

at one terminal of the main chain, and a nitrileoxide group at the otherterminal.

When the polymer comprises, for example, only one polymerizable monomerunit, the polymer can by represented by the following formula:

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) is —R⁴—R^(5′)— wherein R⁴ is a carbon atom having a nitrileoxidegroup;

R³ is —R⁴—R⁶;

R⁴ is a divalent organic group;

R^(5′) is —O—, —S—, —CO—O— or —NR⁹—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms;

R⁶ is a hydrogen atom or an alkyl group having 1-6 carbon atoms;

Mon is ring-opening polymerizable monomer unit;

n is any integer; and

Q is a divalent organic group.

The polymer can be obtained by polymerizing the compound of the formula(I) (provided that, R² is —R⁴—R⁵ and R³ is —R⁴—R⁶) and one or morering-opening polymerizable monomer, and stopping the reaction using acompound having a nitrileoxide group as a terminating agent, orproviding a compound having a precursor group of the nitrileoxide group,and then converting the precursor group into the nitrileoxide group. Inthe formula -Q-CNO is derived from the terminating agent.

Examples of the terminating agent include, but are not particularlylimited, for example, (Ph)₂C═CHNO₂ or (Ph)HC═CHNO₂ wherein Ph is aphenyl group.

For example, when (Ph)₂C═CHNO₂ is used as a terminator agent, a compoundobtained after polymerization is the following compound.

By dehydrating the compound, the following polymer having thenitrileoxide group at both terminals can be obtained.

The present invention provides a polymer comprising one or morering-opening polymerizable monomer units, wherein the polymer comprisesone moiety of the formula (Ic) in the molecular chain:

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R^(2′) and R^(3′) are each independently —R⁴—R^(5′)— wherein R⁴ isattached to a carbon atom having a nitrileoxide group;

R⁴ is a divalent organic group;

R^(5′) is —O—, —S—, —CO—O— or —NR⁹—, preferably —O—;

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms; and

R^(2′) and R³ are directly attached to the ring-opening polymerizablemonomer unit.

When the polymer comprises, for example, only one type of thepolymerizable monomer unit, the polymer can be represented by thefollowing formula:

wherein R¹, R^(2′) and R^(3′) are as defined above,

Mon is a ring-opening polymerizable monomer unit, and

n is each independently any integer.

The copolymer described above can obtained by polymerizing a compound ofthe formula (I) (provided that, both of R² and R² are —R⁴—R⁵) and one ormore ring-opening polymerizable monomer. Therefore, the presentinvention provides a process for producing a polymer comprising one ormore ring-opening polymerizable monomer units and comprising one moietyof the formula (Ic) in the molecular main chain, comprising a step ofpolymerizing one or more ring-opening polymerizable monomer by using acompound of the formula (Ic′) as an initiator:

wherein:

R¹ is a hydrogen atom or a hydrocarbon group;

R² and R³ are each independently, —R⁴—R⁵;

R⁴ is a divalent organic group;

R⁵ is OH, SH, COOH or NHR⁹, preferably OH; and

R⁹ is a hydrogen atom or an alkyl group having 1-6 carbon atoms.

Examples of one or more ring-opening polymerizable monomer used inpreparing of the copolymer include, but are not particularly limited,preferably, monomer able to cause a ring-opening polymerization, forexample, an oxetane, a fluorine-containing oxetane, an epoxy, a cyclicester, and the like.

The monomer unit described above has a structure in which a ring-openingpolymerizable monomer is opened, and includes, for example, thefollowing groups.

—Group Derived from an Epoxy Monomer

—CH(R)CH₂O— wherein R is H or an alkyl group which may be substituted,

—CH₂CH(R)O—

—Group Derived from an Oxetane Monomer

—CH₂CH₂CH₂O— wherein a hydrogen atom may be substituted with afunctional group such as an alkyl group, or the like,

—Group Derived from a Thioether

—CH₂CH(R)S—

—Group Derived from a Cyclic Lactone

—C(O)—(CH₂)_(m)—O— wherein m is an integer of 2-5, and a hydrogen atommay be substituted with another functional group,

—Group Derived from a Cyclic Thiolactone

—C(S)—(CH₂)_(m)—O— wherein m is an integer of 2-5, and a hydrogen atommay be substituted with another functional group,

—Group Derived from a Cyclic Thionolactone

—(CH₂)_(m)—C(O)S— wherein m is an integer of 2-5, and a hydrogen atommay be substituted with another functional group,

—Group Derived from a Glycolide and an Analog Thereof

—C(O)—C(R)O— wherein R is a hydrogen atom or an alkyl group which may besubstituted,

—Group Derived from a Morpholinedione

—C(O)—C(R)NH—C(O)—C(R)O— wherein R is a hydrogen atom or an alkyl groupwhich may be substituted,

—Group Derived from a Cyclic Carbonate or a Lactide

—C(O)O—(CH₂)_(o)—O— wherein o is an integer of 1-4, and a hydrogen atommay be substituted with another functional group,

—Group Derived from a Cyclic Thiocarbonate

—C(S)O—(CH₂)_(o)—O— wherein o is an integer of 1-4, and a hydrogen atommay be substituted with another functional group,

—Group Derived from a Cyclic Thiocarbonate

—(CH₂)O—O—C(O)S— wherein a hydrogen atom may be substituted with anotherfunctional group,

—Group Derived from a Lactam

—NH—C(O)—(CH₂)_(p)— wherein p is an integer of 3-5, and a hydrogen atommay be substituted with another functional group,

—Group Derived from an α-Amino Acid-N-Carboxilic Anhydride (NCA) and anAnalog Thereof

—C(O)—CHR—NH— wherein R is a hydrogen atom or a substituents such as analkyl group, or the like,

—Group Derived from a Cycloalkane

—(CH₂)_(q)—C(EWG)₂- wherein p is an integer of 2-3, EWG is an electronwithdrawing functional group such as CN, C(O)OR, F, Cl, CF₃, NO₂,

—Group Derived from a Cyclobutane

—(CH₂)₂—C(EWG)₂-C(EWG)₂- wherein a hydrogen atom may be substituted withanother functional group, and EWG is an electron withdrawing functionalgroup such as CN, C(O)OR, F, Cl, CF₃, NO₂,

—Group Derived from a Cyclic Trisiloxane

—Si(R)(R′)—O— wherein R and R′ are an alkyl (preferably methyl), phenyl,vinyl, allyl, fluoroalkyl group,

—Group Derived from a Cyclic Siloxane

—Si(R)(R′)O—Si(R)(R′)—NR—Si(R)(R′)O— wherein R, R′ are a substituent,preferably a methyl group, a phenyl group, a vinyl group, an allylgroup, particularly preferably a methyl group,

—Group Derived from 1-Oxa-2,5-Disilacyclopentane

—(CH₂)₂—Si(R)(R′)—O—Si(R″)(R′″)— wherein R, R′, R″ and R′″ are asubstituent, preferably a methyl group, a phenyl group, a naphthylgroup)

—Group Derived from a Silacycloalkane

—Si(R)(R′)—(CH₂)_(q)— wherein a hydrogen atom may be substituted withanother functional group,

—Group Derived from Silacyclopentene

—Si(R)₂—CH₂—CH═CH—CH₂— wherein R is a substituent, preferably a methylgroup,

—Group Derived from a Cyclic Disilane

—Si(R)(R′)—Si(R″)(R′″)— wherein R, R′, R″ and R″′ are a substituent,

—Group Derived from a Cyclic Phosphate Ester, a Cyclic Phosphonate Ester

—P(O)(OR or R)—O(CH₂)_(r)—O— wherein r is an integer of 4-8, R is ahydrogen atom, an alkyl group or an aryl group,

—Copolymer Backbone of an Epoxide or an Oxetane and a Carbon Dioxide,Copolymer Backbone of Ab Episulfide and a Carbon Disulfide

—(CH₂)_(q)—X—C(X)X— wherein X is O or S,

Copolymer of an Epoxide and a Cyclic Acid Anhydride

—(CH₂)₂—O—C(O)—(CH₂)_(q)—C(O)—O—

The polymer of the present invention may has two or more monomer unitsdescribed above.

The compound of the present invention is suitably used in variousapplications, for example, as a hydrophilizing agent, a surface treatingagent, a polymerization initiator, a polymerizable monomer, acrosslinking agent, denaturation treatment agent, thermosetting resin,thermosetting elastomer, liquid rubber, low temperature property rubber,modifier of filler or reactive compatibilizing agent.

The present invention provides a composition comprising the polymer ofthe present invention:

(i) copolymer comprising a monomer unit of the formula (Ia) and one ormore condensation polymerizable or addition polymerizable monomer units,(ii) copolymer comprising a monomer unit of the formula (IIa) and one ormore polymerizable monomer unit,(iii) polymer comprising one or more ring-opening polymerizable monomerunits, which has a group of the formula (Ib) at one terminal of the mainchain,(iv)polymer comprising one or more ring-opening polymerizable monomerunits, which has a group of the formula (Ib) at one terminal of the mainchain, and further has a nitrileoxide group at the other terminal,(v) polymer comprising one or more polymerizable monomer unit, which hasone moiety of the formula (Ia) in the molecular main chain, or(vi) copolymer comprising a monomer unit of the formula (IIIa) and oneor more polymerizable monomer unit.The composition may contain one or more polymers. Furthermore, thecomposition may be composed of only the polymer of the present inventiondescribed above.

The polymer of the present invention (i)-(vi) described above hasusually 1,000 or higher, preferably 2,000 or higher, particularlypreferably 5,000 or higher of a number average molecular weight, but thenumber average molecular weight is not limited thereto, and can beappropriately selected depending on the application. The upper limit ofthe number average molecular weight may be, but not particularlylimited, 2,000,000 or lower, preferably 1,000,000 or lower, andparticularly preferably 500,000 or lower.

In one embodiment, the composition of the present invention may containa material containing a group reactive with a nitrileoxide group inaddition to the composition of the present invention. That is, in thisembodiment, the composition of the present invention may be a mixture ofthe composition of the present invention and the material containing agroup reactive with a nitrileoxide group.

In another embodiment, the composition of the present invention may bein the form of combining with other composition, for example thecomposition containing the material containing a group reactive with anitrileoxide group. In this embodiment, the composition of the presentinvention and other composition may be mixed, preferably mixed justbefore use, and be used in a desired application.

In the above combination form, both the composition of the presentinvention and other composition may be in the form of a liquid, or onemay be in the form of a solid (including a gel), or both may be in theform of a solid (including a gel).

The composition of the present invention may comprise a solvent. Thesolvent can be appropriately selected depending on components containedin the composition.

In a preferable embodiment, the composition of the present invention isused for applying to the material containing a group reactive with anitrileoxide group.

Examples of the “group reactive with a nitrileoxide group” include agroup having a double bond (C═C, C═N, N═N, C═S, P(V)═C, C═P(III), C═As,C═Se, B═N, P(V)═N, C═O), or a group having a triple bond (C≡C, C≡N,C≡P), specifically an alkenyl group, an alkynyl group, and a nitrilegroup.

Examples of the “material” in the material containing a group reactivewith a nitrileoxide group include, but are not particularly limited to,for example, glass materials, resin materials, compounds which is ableto be applied with a crosslinking agent, in particular polymericcompounds (for example, natural rubbers, synthetic rubbers), and variouscompounds.

The polymer contained the composition of the present invention containsa nitrileoxide group, thus has high reactivity, thereby being able tomodify various base material, compounds, etc., and to provide them withdesired property.

In particular, (i) a composition comprising a copolymer comprising amonomer unit of the formula (Ia) and one or more condensationpolymerizable or addition polymerizable monomer units, and (ii) acomposition comprising a copolymer comprising a monomer unit of theformula (IIa) and one or more radical polymerizable monomer units, and(iv) a composition comprising a polymer comprising one or morering-opening polymerizable monomer units, which has a group of theformula (Ib) at the terminal of the main chain, and a nitrileoxide groupat the other terminal may be useful as a crosslinking agent. In thiscase, in particular, (i) and (ii) compositions are preferable.

In particular, (iii) a composition comprising a polymer comprising oneor more ring-opening polymerizable monomer units, which has a group ofthe formula (Ib) at one terminal or both terminals of the main chain,and (iv) a composition comprising a polymer comprising one or morering-opening polymerizable monomer units, which has one moiety of theformula (Ia) in the main chain may be useful as a grafting agent. Inthis case, in particular, (iii) a composition comprising a polymercomprising one or more radical polymerizable monomer units, has a groupof the formula (Ib) at one terminal of the main chain and (iv)composition are preferable.

In one embodiment, the composition of the present invention is ahydrophilizing agent.

The hydrophilizing agent of the present invention comprises at least onepolymer having a group of the formula (Ib) at the terminal of the mainchain of the present invention.

The base material applied with the hydrophilizing agent of the presentinvention is not limited as long as it has a reactive group with thenitrileoxide group. For example, by reacting the hydrophilizing agent ofthe present invention with a compound having low hydrophilic, thehydrophilic of the compound can be increased. In addition, by reactingthe hydrophilizing agent of the present invention with a surface of anon-hydrophilic resin, the hydrophilic of the surface of the resin canbe increased.

In one embodiment, the hydrophilization described above can be performedby mixing the composition of the present invention and other polymericmaterial or molding (preferably film-forming) other polymeric material,and applying the composition of the present invention to the surfacethereof.

In a preferable embodiment, the hydrophilized polymeric material ismolded into a porous polymer membrane.

Therefore, the present invention provides a membrane composed from amixture of the compound of the present invention and other polymericmaterial.

In a preferable embodiment, the other polymeric materials arefluorine-containing polymer, typically a vinylidene fluoride polymer,preferably polyvinylidene fluoride or a copolymer having a vinylidenefluoride unit.

The compounds of the present invention can be added to thefluorine-containing polymer such that its concentration is 0.5 to 50% bymass to provide a composition. A more preferable lower limit is 5% byweight, more preferable lower limit is 10% by mass, and a morepreferable upper limit is 30% by mass.

When the fluorine-containing polymer is a vinylidene fluoride polymer,it is possible to mix it with the compounds of the present invention bymelt-kneading, thereby forming a porous polymer membrane havingexcellent properties. In this respect, the composition is preferably acomposition obtained by melt-kneading the compound of the presentinvention and polyvinylidene fluoride or a copolymer having a vinylidenefluoride unit.

The weight average molecular weight of the polyvinylidene fluoride is,from the viewpoint of mechanical strength and processability of thepolymer porous membrane, preferably 30,000 to 2,000,000, more preferably50,000 to 1,000,000.

The vinylidene fluoride polymer may be a homopolymer consisting ofvinylidene fluoride units, or may be a modified polymer comprising avinylidene fluoride unit and other monomer unit. In the modifiedpolymer, as the other monomer, a monomer copolymerizable with vinylidenefluoride can be used, and examples of the other monomer includetetrafluoroethylene (TFE), hexafluoropropene (HFP),chlorotrifluoroethylene (CTFE), trifluoroethylene, perfluoroalkyl vinylethers, fluoroalkyl ethylene, trifluoro propylene, pentafluoropropylene,trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, afluoromonomer of the general formula: CH₂═CFRf (wherein Rf is a linearor branched fluoroalkyl group having 1 to 12 carbon atoms), and thelike. In polyvinylidene fluoride, the molar ratio of the vinylidenefluoride unit and the other monomeric units (vinylidene fluorideunit/other monomer units) is preferably greater than 99/1 and less than100/0.

Examples of the copolymer including a vinylidene fluoride unit includevinylidene fluoride/tetrafluoroethylene copolymers and vinylidenefluoride/hexafluoropropylene copolymers. In order to achieve goodmechanical strength and alkali resistance, the copolymer including avinylidene fluoride unit is particularly preferably a vinylidenefluoride/tetrafluoroethylene copolymer.

In order to achieve good membrane formability and alkali resistance, thevinylidene fluoride/tetrafluoroethylene copolymer preferably satisfies aratio by mole between the vinylidene fluoride unit and thetetrafluoroethylene unit (vinylidene fluoride unit/tetrafluoroethyleneunit) of 50 to 99/50 to 1. Examples of such a polymer include VT series(DAIKIN INDUSTRIES, Ltd.). The ratio by mole between the vinylidenefluoride unit and the tetrafluoroethylene unit in the vinylidenefluoride/tetrafluoroethylene copolymer is more preferably 50 to 95/50 to5, still more preferably 50 to 90/50 to 10. In addition to thevinylidene fluoride/tetrafluoroethylene copolymer consisting only of avinylidene fluoride unit and a tetrafluoroethylene unit, the vinylidenefluoride/tetrafluoroethylene copolymer may be a ternary or highercopolymer having not only a vinylidene fluoride unit and atetrafluoroethylene unit but also any other units such as ahexafluoropropylene unit, a chlorotrifluoroethylene unit, and aperfluorovinyl ether unit to the extent that these units do notdeteriorate the characteristics

The weight average molecular weight of the copolymer including avinylidene fluoride unit varies in accordance with the application ofthe resulting porous polymer membrane. In order to achieve goodmechanical strength and membrane formability, the weight averagemolecular weight thereof is preferably 10,000 or more. It is morepreferably 30,000 to 2,000,000, still more preferably 50,000 to1,000,000, particularly preferably 100,000 to 800,000. The weightaverage molecular weight can be determined by gel permeationchromatography (GPC).

In one embodiment, the other polymeric material may comprise a resinother than vinylidene fluoride polymer.

Examples of the resin other than vinylidene fluoride polymer includepolyethylene resin, polypropylene resin, acrylic resin,polyacrylonitrile, acrylonitrile-butadiene-styrene (ABS) resin,polystyrene resin, acrylonitrile-styrene (AS) resin, vinyl chlorideresin, polyethylene terephthalate, polyamide resin, polyacetal resin,polycarbonate resin, modified polyphenylene ether resin, polyphenylenesulfide resin, polyamide imide resin, polyether imide resin, polysulfoneresin, polyether sulfone resin, and mixtures and copolymers thereof.Resin miscible with these resins may also be mixed.

The resin other than vinylidene fluoride polymer is preferably at leastone selected from the group consisting of a polyethylene resin, apolypropylene resin, and an acrylic resin.

The polyethylene resin is a resin comprising an ethylene homopolymer oran ethylene copolymer. The polyethylene resin may comprise multipleethylene copolymers. Examples of the ethylene copolymer includecopolymers of ethylene and at least one selected from unsaturated linearhydrocarbons such as propylene, butene, and pentene.

The polypropylene resin is a resin comprising a propylene homopolymer ora propylene copolymer. The polypropylene resin may comprise multiplepropylene copolymers. Examples of the propylene copolymer includecopolymers of propylene and at least one selected from the groupconsisting of unsaturated linear hydrocarbons such as ethylene, butene,and pentene.

The acrylic resin is a polymeric compound mainly containing acrylicacid, methacrylic acid or a derivative thereof, such as a polymer ofacrylamide or acrylonitrile. Particularly preferred are acrylate resinand methacrylate resin.

The resin other than vinylidene fluoride polymer is most preferablyacrylic resin.

The characteristics of the resulting porous polymer membrane such asmembrane strength, water permeability, and the blocking performance canbe adjusted by adjusting the type and the amount of the resin other thanvinylidene fluoride polymer.

In order to achieve hydrophilization, to control phase separation, andto improve the mechanical strength, the composition of the presentinvention may further contain additives such as polyvinylpyrrolidone,polymethyl methacrylate resin, polyethylene glycol, montmorillonite,SiO₂, TiO₂, CaCO₃, and polytetrafluoroethylene

The porous polymer membrane described above can be produced by any ofvarious methods. Examples thereof include phase separation, meltextraction, vapor solidification, stretching, etching, sintering of apolymer sheet into a porous membrane, crushing of a bubble-containingpolymer sheet into a porous membrane, and electrospinning.

The melt extraction is a method of forming a porous structure bymelt-kneading inorganic particles and organic liquid matter with amixture; extrusion-molding the kneaded matter through a die or moldingit with a press at a temperature not lower than the melting points ofthe compound of the present invention and the fluorine-containingpolymer; cooling and solidifying the molded article; and then extractingthe organic liquid matter and the inorganic particles.

The vapor solidification is a method of forcedly supplying saturatedvapor or vapor containing mist of one or both of a nonsolvent and a poorsolvent which are compatible with a good solvent and do not dissolve thecompound of the present invention and the fluorine-containing polymerfor at least one surface of a membrane-like article formed from acomposition prepared by dissolving the compound of the present inventionand the fluorine-containing polymer in a good solvent.

In a preferable embodiment, the porous polymer membrane of the presentinvention is preferably produced by the phase separation because thepore size is easily controlled. Examples of the phase separation includethermally induced phase separation (TIPS) and nonsolvent-induced phaseseparation (NIPS).

In the case of thermally induced phase separation, the porous polymermembrane of the present invention can be produced by a method includinga step of dissolving the compound of the present invention and thefluorine-containing polymer in a solvent that is a poor solvent or agood solvent at a relatively high temperature to provide a composition,and a step of cooling and solidifying the composition.

The composition prepared by dissolving the compound of the presentinvention and the fluorine-containing polymer in a solvent is in theform of a uniform single-phase liquid when it is maintained at atemperature higher than what is called a cloud point. In contrast, phaseseparation occurs at a temperature not higher than the cloud point sothat the composition is separated into two phases, i.e., a polymer-richphase and a solvent-rich phase. When the temperature reaches thecrystallization temperature or lower, the polymer matrix is immobilized,so that a porous membrane is formed.

In the case of thermally induced phase separation, the sum of theamounts of the compound of the present invention and thefluorine-containing polymer in the composition is preferably 10 to 60%by mass relative to the sum of the amounts of the compound of thepresent invention and the fluorine-containing polymer, and the solvent.It is more preferably 15 to 50% by mass.

The viscosity of the composition can be adjusted within an appropriaterange by adjusting the concentration of the compound of the presentinvention and the fluorine-containing polymer within an appropriaterange. If the viscosity of the composition is beyond an appropriaterange, the porous polymer membrane may not be formed

The poor solvent is a solvent that is not capable of dissolving 5% bymass or more of the compound of the present invention and thefluorine-containing polymer at a temperature lower than 60° C. butcapable of dissolving 5% by mass or more thereof at a temperature of 60°C. or higher and not higher than the melting points of the resins. Incontrast to the poor solvent, a solvent that is capable of dissolving 5%by mass or more of the resins even at a temperature lower than 60° C. iscalled a good solvent. A solvent that neither dissolves nor swells theresins until the temperature reaches the melting points of the resins orthe boiling point of the liquid is called a nonsolvent.

Examples of the poor solvent include middle-chain-length alkyl ketones,esters, glycol esters and organic carbonates such as cyclohexanone,isophorone, γ-butyrolactone, methyl isoamyl ketone, dimethyl phthalate,diethyl phthalate, dibutyl phthalate, aliphatic polyhydric alcohols,propylene glycol methyl ether, propylene carbonate, diacetone alcohol,and glycerol triacetate, and solvent mixtures thereof. Fluorosolventssuch as HFC-365, diphenyl carbonate, methyl benzoate, diethylene glycolethyl acetate, or benzophenone may also be used. Even with respect to asolvent mixture of a nonsolvent and a poor solvent, a solvent thatsatisfies the definition of a poor solvent is defined as a poor solvent.

In the case of thermally induced phase separation, a solvent for thecomposition is preferably, but not limited to, a poor solvent. As aresult of examining the behavior of phase separation of a fluoropolymer,a good solvent may be used in some cases.

Examples of the good solvent include fluorosolvents such as HCFC-225,lower alkyl ketones, esters, and amides such as N-methyl-2-pyrrolidone,dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, methyl ethylketone, acetone, methanol, tetrahydrofuran, tetramethylurea, andtrimethyl phosphate, and solvent mixtures thereof.

Examples of the nonsolvent include water, aliphatic hydrocarbons,aromatic hydrocarbons, aromatic polyhydric alcohols, and chlorinatedhydrocarbons or other chlorinated organic liquids such as hexane,pentane, benzene, toluene, carbon tetrachloride, o-dichlorobenzene,trichloroethylene, ethylene glycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, propylene glycol, butylene glycol, pentanediol, hexane diol, methanol, ethanol, propanol, and low molecular weightpolyethylene glycol, and solvent mixtures thereof.

In the case of thermally induced phase separation, the step of providinga composition is preferably a step of dissolving the compound of thepresent invention and the fluorine-containing polymer in a solvent thatis a poor solvent or a good solvent at 20° C. to 270° C. The dissolvingtemperature is preferably 30° C. to 250° C. When dissolved at arelatively high temperature, the compound of the present invention andthe fluorine-containing polymer can be at a high concentration. Thisenables production of a porous polymer membrane having high mechanicalstrength. If the concentration of the compound of the present inventionand the fluorine-containing polymer is too high, the resulting porouspolymer membrane may have a low porosity, resulting in poor waterpermeability. If the viscosity of the prepared composition is beyond anappropriate range, a porous membrane may not be formed.

The composition is preferably cooled and solidified by a method ofejecting the composition into a cooling bath through a die, for example.For the porous polymer membrane in the form of a flat membrane, a methodof casting and immersing the composition in a cooling bath is also onepreferable method.

Those able to be used as a cooling liquid for the cooling bath have atemperature lower than that of the composition. Examples thereof includea liquid containing a solvent that is a poor solvent or a good solventat a temperature of 0° C. to 80° C. and a concentration of 60 to 100% bymass. The cooling liquid may be a nonsolvent or a nonsolvent containinga poor solvent or a good solvent.

In the production of the porous polymer membrane of the presentinvention, important features are the concentration of the composition,the constitution of the solvent that dissolves the compound of thepresent invention and the fluorine-containing polymer, and theconstitution of the cooling liquid constituting the cooling bath. Theporous structure of the porous polymer membrane can be adjusted byadjusting these compositions.

For example, one surface and the other surface of the porous polymermembrane may have different combinations of the constitution of thecomposition and the constitution of a cooling liquid. Thereby, thestructure of the one surface of the porous polymer membrane may be madedifferent from the structure of the other surface.

In producing the porous polymer membrane by nonsolvent-induced phaseseparation, for example, the porous polymer membrane is preferablyproduced by a method including a step of dissolving the compound of thepresent invention and the fluorine-containing polymer in a solvent toprovide a composition, and a step of ejecting the composition into asolidification bath containing a nonsolvent through a die.

Immersion of the composition in a solidification bath containing anonsolvent can cause nonsolvent-induced phase separation with theconcentration gradient between the solvent and nonsolvent in thecomposition and the solidification bath used as a power for phaseseparation. In such a method, a fine skin layer is first formed on theouter surface where phase separation occurs due to replacement betweenthe solvent and the nonsolvent. Then, the phase-separating phenomenonproceeds toward the inside of the membrane. As a result, after theformation of the skin layer, an asymmetric membrane can also be producedin which the pore size continually increases toward the inside of themembrane.

In the case of nonsolvent-induced phase separation, the compositionpreferably comprises the compound of the present invention, thefluorine-containing polymer, and the solvent. The composition furthercomprising a nonsolvent in addition to the compound of the presentinvention, the fluorine-containing polymer, and the solvent is also onepreferable embodiment.

The composition preferably contains 5 to 60% by mass of the compound ofthe present invention, and the fluorine-containing polymer relative tothe sum of the amounts of the compound of the present invention, thefluorine-containing polymer, the solvent, and the nonsolvent (if thecomposition contains no nonsolvent, the sum of the amounts of thecompound of the present invention, the fluorine-containing polymer, andthe solvent). This value is more preferably 10 to 50% by mass.

The composition preferably contains 0.1 to 10% by mass of the nonsolventrelative to the sum of the amounts of the compound of the presentinvention, the fluorine-containing polymer, the solvent, and thenonsolvent. This value is more preferably 0.5 to 8% by mass. Theviscosity of the composition can be adjusted within an appropriate rangeby adjusting the fluoropolymer concentration within an appropriaterange. If the viscosity of the composition is beyond an appropriaterange, a porous polymer membrane may not be formed.

The composition may be at room temperature or may be heated. Forexample, the composition is preferably at 10° C. to 75° C.

The solvent to be used in nonsolvent-induced phase separation may be anysolvent exemplified for thermally induced phase separation. The solventmay be either a poor solvent or a good solvent, and is preferably a goodsolvent. The nonsolvent may be any nonsolvent exemplified for thermallyinduced phase separation.

With respect to a solidification liquid to be used as the solidificationbath, solidification is preferably achieved using a liquid containing anonsolvent. The liquid may further contain a poor solvent and a goodsolvent. The nonsolvent may be any nonsolvent exemplified for thermallyinduced phase separation. For example, water may suitably be used.

In production of the porous polymer membrane of the present invention,the thermally induced phase separation and the nonsolvent-induced phaseseparation may be used in combination.

The nonsolvent-induced phase separation and the thermally induced phaseseparation can provide a porous membrane by ejecting a compositionprepared by dissolving the compound of the present invention, thefluorine-containing polymer in a solvent through a die and solidifyingthe composition. Examples of the die include slit dies, double orificespinnerets, and triple orifice spinnerets.

In the case of producing a porous polymer membrane in the form of ahollow fiber membrane, the die to be used is preferably a double orificespinneret or a triple orifice spinneret for spinning hollow fibermembranes.

In the case of a double orifice spinneret, the composition is emittedfrom the outer tube of the double orifice spinneret, while ahollow-forming fluid such as ion exchange water is emitted from theinner tube, and then the composition is solidified in a solidificationbath or a cooling bath. Thereby, a hollow fiber membrane can beproduced.

The hollow-forming fluid is usually in the form of gas or liquid. Inthermally induced phase separation, a liquid containing a poor solventor a good solvent at a concentration of 60 to 100%, which is the same asthe cooling liquid, can preferably be used. Alternatively, a nonsolventor a nonsolvent containing a poor solvent or a good solvent may also beused. In the nonsolvent-induced phase separation, the hollow-formingfluid is preferably the aforementioned nonsolvent. For example, watersuch as ion exchange water is preferred. The aforementioned nonsolventmay contain a poor solvent or a good solvent.

In thermally induced phase separation, the hollow-forming fluid ispreferably the aforementioned solvent. For example, a poor solvent suchas glycerol triacetate is preferred. In thermally induced phaseseparation, nitrogen gas may also be used.

A hollow fiber membrane with two structures may be formed by varying theconstitution of a hollow-forming fluid and of a cooling liquid orsolidification liquid. The hollow-forming fluid may be supplied in thecooled state. If the cooling force of the cooling bath alone issufficient for solidifying the hollow fiber membrane, the hollow-formingfluid may be supplied without cooling.

A triple orifice spinneret is suitable for the cases of using two resinsolutions. For example, two compositions are emitted from the outer tubeand the middle tube, respectively, of the triple orifice spinneret,while a hollow-forming liquid is emitted from the inner tube, and thenthe compositions are solidified in a solidification bath or a coolingbath. Thereby, a hollow fiber membrane can be formed. Alternatively, acomposition is emitted from the outer tube of the triple orificespinneret, a resin solution containing a resin other than the compoundof the present invention, the fluorine-containing polymer is emittedfrom the middle tube, and a hollow-forming fluid is emitted from theinner tube, while the emitted materials are solidified in asolidification bath or a cooling bath. Thereby, a hollow fiber membranecan be formed. The resin other than the compound of the presentinvention, the fluorine-containing polymer may be any of those mentionedabove. Preferred is the aforementioned thermoplastic resin, and morepreferred is acrylic resin.

As mentioned above, production of a hollow fiber membrane by a methodusing a double orifice spinneret or a triple orifice spinneret ispreferred in that the amount of a solidification liquid or a coolingliquid can be smaller than in production of a flat membrane.

The porous polymer membrane of the present invention in the form of ahollow fiber membrane may further have a fluoropolymer layer or a resinlayer of a resin other than the compound of the present invention, thefluorine-containing polymer on the outer surface or the inner surface ofthe hollow fiber membrane formed by the above method.

The fluoropolymer layer or the resin layer can be formed by applying acomposition or a resin solution to the outer surface or the innersurface of the hollow fiber membrane. A method of applying thecomposition or the resin solution to the outer surface of the hollowfiber membrane is preferably immersing the hollow fiber membrane in thecomposition or the resin solution or dropping the composition or theresin solution onto the hollow fiber membrane. A method of applying thecomposition or the resin solution to the inner surface of the hollowfiber membrane is preferably injecting the composition or the resinsolution into the hollow fiber membrane. The amount of the compositionor the resin solution to be applied can preferably be controlled by amethod of controlling the amount itself of the composition or the resinsolution to be applied, as well as a method of partially scraping off orblowing with an air knife the composition or the resin solution afterimmersing the porous membrane in the composition or the resin solutionor applying the composition or the resin solution to the porousmembrane, or a method of adjusting the concentration thereof uponapplication.

The porous polymer membrane in the form of a flat membrane can beproduced by casting the composition and immersing the composition in acooling bath or a solidification bath. Alternatively, such a membranecan be produced by ejecting the composition into a cooling bath or asolidification bath through a slit die.

The porous polymer membrane in the form of a composite membranecomprising a porous base can be produced by immersing a porous base inthe composition or by applying the composition to at least one face of aporous base, for example.

The aforementioned production method can provide a porous polymermembrane having low contact angle. Still, if the water permeability isinsufficient, the porous membrane produced by the above productionmethod may be further stretched so that the porous polymer membrane ofthe present invention can be obtained.

The pore size of the porous polymer membrane can be controlled by, forexample, mixing an additive for controlling the pore size with thecomposition, and then allowing the additive to be eluted during or afterformation of the porous structure of the compound of the presentinvention, the fluorine-containing polymer. The additive may be made toremain in the porous membrane.

In each of the nonsolvent-induced phase separation and the thermallyinduced phase separation, the composition may contain an additive.Elution of the additive after formation of the porous structure enablescontrol of the pore size of the porous polymer membrane. The additivemay be made to remain in the porous membrane, if necessary.

Examples of the additive include organic compounds and inorganiccompounds. The organic compounds are preferably those dissolved oruniformly dispersed in a solvent constituting the composition. They arealso preferably those dissolved in a nonsolvent contained in thesolidification liquid for nonsolvent-induced phase separation or asolvent contained in the cooling liquid for thermally induced phaseseparation.

Examples of the organic compounds include water-soluble polymers such aspolyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol,polyethylene imine, polyacrylic acid, and dextran, surfactants such asTween 40 (polyoxyethylene sorbitan monopalmitate), glycerin, andsaccharides.

The inorganic compounds are preferably water-soluble compounds. Examplesthereof include calcium chloride, lithium chloride, and barium sulfate.

The average pore size on the surface can also be controlled bycontrolling the phase separation rate in accordance with the type,concentration, and temperature of a nonsolvent in the solidificationliquid without any additive. In general, the higher the phase separationrate is, the smaller the average pore size on the surface is, whereasthe lower the rate is, the larger the size is. Addition of a nonsolventto the composition is also effective to control the phase separationrate.

In order to achieve hydrophilization, to control phase separation, andto improve mechanical strength, the composition may further contain anyadditives such as polyvinylpyrrolidone, polymethyl methacrylate resin,montmorillonite, SiO₂, TiO₂, CaCO₃, and polytetrafluoroethylene.

In order to improve the water permeability, the porous polymer membranemay be treated with an alkali. The alkali herein means a NaOH aqueoussolution, a KOH aqueous solution, ammonia water, an amine solution, orthe like. They may contain any alcohol such as ethanol and methanol, andorganic solvents. The alkali preferably contains an alcohol, but it isnot limited thereto.

By applying the compound of the present invention to the porous polymermembrane, the compound can form a coating to provide hydrophilicity. Asthe porous polymer membrane, those described above are able to be used.

Therefore, the present invention provides a membrane obtained byapplying the compound of the present invention to the surface of themembrane of the other polymeric material.

The compound of the present invention may contain an organic solvent,and when the compound contains the organic solvent, it is possible toeasily applied.

Examples of the organic solvent include the following solvents:

aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene andsolvent naphtha;

esters such as methyl acetate, ethyl acetate, propyl acetate, n-butylacetate, isobutyl acetate, isopropyl acetate, isobutyl acetate,cellosolve acetate, propylene glycol methyl ether acetate, carbitolacetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethylacetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate;

ketones such as acetone, methyl ethyl ketone, cyclohexanone, methylisobutyl ketone, cyclohexanone, methyl isobutyl ketone, 2-hexanone,cyclohexanone, methyl amino ketone and 2-heptanone;

glycol ethers such as ethyl cellosolve, methyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonobutyl ether, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, propylene glycol monobutyl etheracetate, dipropylene glycol dimethyl ether and ethylene glycol monoalkylether;

alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol,tert-butanol, sec-butanol, 3-pentanol, octyl alcohol,3-methyl-3-methoxybutanol and tert-amyl alcohol;

cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane;amides such as N,N-dimethylformamide and N,N-dimethylacetamide;

ether alcohols such as methyl cellosolve, cellosolve, isopropylcellosolve, butyl cellosolve and diethylene glycol monomethyl ether;

1,1,2-trichloro-1,2,2-trifluoroethane,1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, and thelike. Also, there are solvent mixtures of two or more thereof.

Examples of the fluorine-containing solvent include the followingsolvents:

for example, CH₃CCl₂F (HCFC-141b), CF₃CF₂CHCl₂/CClF₂CF₂CHClF mixture(HCFC-225), perfluorohexane, perfluoro(2-butyltetrahydrofuran),methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, and inaddition, fluorine-containing alcohols such as H(CF_(2c)F₂)_(n)CH₂OH (n:an integer of 1-3), F(CF₂)_(n)CH₂OH (n: an integer of 1-5),CF₃CH(CF₃)OH; benzotrifluoride, perfluorobenzene,perfluoro(tributylamine), ClCF₂CFClCF₂CFCl₂, and the like.

The fluorine-containing solvent may be single, or a mixed solvent of thefluorine-containing solvents or a fluorine-free solvent and one or morefluorine-containing solvents. Among them, alcohol and ketone, butylacetate, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethylsulfoxide is preferable, furthermore iso-propanol and methyl ethylketone, methyl isobutyl ketone, N,N-dimethylformamide,N,N-dimethylacetamide, dimethylsulfoxide is most preferable. When thecompound of the present invention contains the organic solvent, thecompound preferably contains the above-mentioned fluorine-containingsolvent at 5-60% by mass. Applying of hydrophilizing agent is able to beperformed by a known method, for example, a spin coating method, a barcode method, a casting method, a spray method, an electrospinningmethod, or the like. The compound of the present invention may furthercontain additives usually used in paints, such as curing agents, curingaccelerators, pigments, dispersants, thickeners, preservatives,ultraviolet absorbers, antifoaming agents, conventional additives,leveling agents, or the like.

The porous polymer membrane is suitable for drinking water production,water treatment, a microfiltration membrane or ultrafiltration membraneused in water treatment of waste water treatment and the like. Theporous polymer membrane is particularly preferably a porous polymermembrane for the water treatment.

In addition, the p porous polymer membrane is suitably used also in thefood field, battery field, or the like.

In the food field, the porous polymer membrane can be used for thepurpose of separation of yeast used in the fermentation, orconcentration of liquid.

In the battery field, the porous polymer membrane can be used as abattery separator to which electrolytes can permeate and productsgenerated in cell reaction cannot permeate.

In one embodiment, the composition of the present invention is a surfacetreatment agent.

The surface treatment agent of the present invention comprises at leastone polymer having a group of the formula (Ib) at the terminal of themain chain of the present invention as a main ingredient or an activeingredient, and can form surface-treating layer having water-repellency,oil-repellency, antifouling property, friction durability, surface slipproperty, water-proof property or the like, thus is used as anantifouling coating agent or a water-proof coating agent. The “mainingredient” means an ingredient whose contents is more than 50% in thesurface treatment agent, and the “active ingredient” means an ingredientwhich remains on a material to be surface-treated to form asurface-treating layer, thereby exhibiting some function(water-repellency, oil-repellency, antifouling property, surface slipproperty, friction durability, etc.).

The surface treatment agent of the present invention has an advantageousthan a surface treatment agent containing a fluorine-containing silanecompound which is suitably applied mainly to a glass material, and asurface treatment agent containing a compound having a curable moiety(for example, double bond) which is suitably applied mainly to a resinmaterial in point that it can be suitably applied to any base materialas long as it is reactive with a nitrileoxide group.

The composition of the surface treatment agent of the present inventionmay be selected depending on a function which is desired in thesurface-treating layer.

For example, the surface treatment agent may comprise a fluoropolyethercompound which may be also understood as a fluorine-containing oil,preferably a perfluoro(poly) ether compound (hereinafter, referred to asa “fluorine-containing oil”) in addition to the polymer having a groupof the formula (Ib) at the terminal of the main chain of the presentinvention. The fluorine-containing oil contributes to increasing ofsurface slip property of the surface-treating layer.

The fluorine-containing oil may be contained in the surface-treatingagent of the present invention, for example, at 0-300 parts by mass,preferably 50-200 parts by mass with respect to 100 parts by mass of thepolymer having a group of the formula (Ib) at the terminal of the mainchain of the present invention (as the total mass when two or morecompounds are used; hereinafter the same shall apply).

Examples of the above-mentioned fluorine-containing oil include, but arenot particularly limited to, for example, a compound (aperfluoropolyether compound) of the following general formula (A).

R²¹—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—R²²  (A)

In the formula, R²¹ represents an alkyl group having 1-16 carbon atomswhich may be substituted by one or more fluorine atoms, preferably analkyl group having 1-3 carbon atoms which may be substituted by one ormore fluorine atoms. Preferably, the alkyl which may be substituted byone or more fluorine atoms is a fluoroalkyl group in which a terminalcarbon atom is CF₂H— and the other carbon atoms are fully substituted bya fluorine atom, or a perfluoroalkyl group, more preferably aperfluoroalkyl group.

R²² represents a hydrogen atom, a fluorine atom, or an alkyl grouphaving 1-16 carbon atoms which may be substituted by one or morefluorine atoms, preferably an alkyl group having 1-3 carbon atoms whichmay be substituted by one or more fluorine atoms. Preferably, the alkylwhich may be substituted by one or more fluorine atoms is a fluoroalkylgroup in which a terminal carbon atom is CF₂H— and the other carbonatoms are fully substituted by a fluorine atom, or a perfluoroalkylgroup, more preferably a perfluoroalkyl group.

Subscripts a′, b′, c′ and d′ represent the repeating number of each ofthree repeating units of perfluoropolyether which constitute a mainbackbone of the polymer, and are each independently an integer of 0 ormore and 300 or less, and the sum of a′, b′, c′ and d′ is at least 1,preferably 1-100. The occurrence order of the respective repeating unitsin parentheses with the subscript a′, b′, c′ or d′ is not limited in theformula. Among these repeating units, the —(OC₄F₈)— group may be any of—(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂C_(F)C₂)—, —(OCF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—, —(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F) CF₂)— and —(OCF₂CF(C₂F₅))—, preferably—(OCF₂CF₂CF₂CF₂). The —(OC₃F₆)— group may be any of —(OCF₂CF₂CF₂)—,—(OCF(CF₃) CF₂)— and —(OCF₂CF(CF₃))—, preferably —(OCF₂CF₂CF₂)—. The—(OC₂F₄)— group may be any of —(OCF₂CF₂)— and —(OCF(CF₃))—, preferably—(OCF₂CF₂)—.

Examples of the perfluoropolyether compound of the above general formula(A) include a compound of any of the following general formulae (A1) and(A2) (may be one compound or a mixture of two or more compounds).

R²¹—(OCF₂CF₂CF₂)_(b″)—R²²  (A1)

R²¹—(OCF₂CF₂CF₂CF₂)_(a″)—(OCF₂CF₂CCF)_(b″)—(OCF₂CF₂)_(c″)—(OCF₂)_(d″)—R²²  (A2)

In these formulae:

R²¹ and R²² are as defined above; in the formula (A1), b″ is an integerof 1 or more and 100 or less; and in the formula (A2), a″ and b″ areeach independently an integer of 1 or more and 30 or less, and c″ and d″are each independently an integer of 1 or more and 300 or less. Theoccurrence order of the respective repeating units in parentheses withthe subscript a″, b″, c″ or d″ is not limited in the formulae.

The compound of the general formula (A1) and the compound of the generalformula (A2) may be used alone or in combination.

When the polymer having a group of the formula (Ib) at the terminal ofthe main chain of the present invention contains a perfluoroalkyl group,the fluorine-containing oil may be a compound of the general formulaRf¹-F wherein Rf¹ is a perfluoroalkyl group contained in the polymer ofthe present invention. In this case, the compound of Rf¹-F is preferablebecause the compound has high affinity for the polymer of the presentinvention.

The surface treatment agent may comprise a silicone compound which maybe also understood as a silicone oil (hereinafter referred to as a“silicone oil”) in addition to the polymer having a group of the formula(Ib) at the terminal of the main chain of the present invention. Thesilicone oil contributes to increasing of surface slip property of thesurface-treating layer.

The silicone oil may be contained in the surface treatment agent, forexample, at 0-300 parts by mass, preferably 50-200 parts by mass withrespect to 100 parts by mass of the polymer having a group of theformula (Ib) at the terminal of the main chain of the present invention.

Examples of the above-mentioned silicone oil include, for example, aliner or cyclic silicone oil having 2,000 or less siloxane bonds. Theliner silicone oil may be so-called a straight silicone oil and amodified silicon oil. Examples of the straight silicone oil includedimethylsilicone oil, methylphenylsilicone oil, andmethylhydrogensilicone oil. Examples of the modified silicone oilinclude that which is obtained by modifying a straight silicone oil withalkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino,epoxy, carboxyl, alcohol, or the like. Examples of the cyclic siliconeoil include, for example, cyclic dimethylsiloxane oil.

The present invention also provides an article comprising a basematerial and a layer (a surface-treating layer) which is formed from thepolymer having a group of the formula (Ib) at the terminal of the mainchain of the present invention or the surface treatment agent(hereinafter, representatively referred to as a “surface-treatingcomposition”) on the surface of the base material. This article can beproduced, for example, as follows.

Firstly, the base material is provided. As mentioned above, the surfacetreatment agent of the present invention can be suitably applied to anybase material as long as it has reactivity with a nitrileoxide group.The base material usable in the present invention may be composed of anysuitable material such as a glass, a resin (may be a natural orsynthetic resin such as a common plastic material, and may be in form ofa plate, a film, or others), a metal (may be a simple substance of ametal such as aluminum, copper, or iron, or a complex such as alloy orthe like), a ceramic, a semiconductor (silicon, germanium, or the like),a fiber (a fabric, a non-woven fabric, or the like), a fur, a leather, awood, a pottery, a stone, or the like.

For example, when an article to be produced is an optical member, amaterial constituting the surface of the base material may be a materialfor an optical member, for example, a glass or a transparent plastic.For example, when an article to be produced is an optical member, anylayer (or film) such as a hard coating layer or an antireflection layermay be formed on the surface (outermost layer) of the base material. Asthe antireflection layer, either a single antireflection layer or amulti antireflection layer may be used. Examples of an inorganicmaterial usable in the antireflection layer include SiO₂, SiO, ZrO₂,TiO₂, TiO, Ti₂O₃, Ti₂O₅, Al₂O₃, Ta₂O₅, CeO₂, MgO, Y₂O₃, SnO₂, MgF₂, WO₃,and the like. These inorganic materials may be used alone or incombination with two or more (for example, as a mixture). Furthermore,the base material may have an insulating layer, an adhesive layer, aprotecting layer, a decorated frame layer (I-CON), an atomizing layer, ahard coating layer, a polarizing film, a phase difference film, a liquidcrystal display module, and the like, depending on its specificspecification.

The shape of the base material is not particularly limited. The regionof the surface of the base material on which the surface-treating layershould be formed may be at least a part of the surface of the basematerial, and may be appropriately determined depending on use, thespecific specification, and the like of the article to be produced.

The base material may be that of which at least the surface consists ofa material originally having a group reactive with a nitrileoxide group.On the other hand, by pre-treating the base material, the group reactivewith a nitrileoxide group may be introduced to the base material. Forexample, when the base material is a glass, the group reactive with anitrileoxide group can be introduced to the base material by treatingthe base material with a piranha solution to express a hydroxyl group,and reacting this hydroxyl group for example with allyltrichlorosilane.

Next, the film of the above surface-treating agent of the presentinvention is formed on the surface of the base material, and the film ispost-treated, as necessary, and thereby the surface-treating layer isformed from the surface-treating agent.

The formation of the film of the surface-treating agent of the presentinvention can be performed by applying the above surface-treating agenton the surface of the base material such that the surface-treating agentcoats the surface. The method of coating is not particularly limited.For example, a wet coating method or a dry coating method can be used.

Examples of the wet coating method include dip coating, spin coating,flow coating, spray coating, roll coating, gravure coating,micro-gravure coating, bar coating, die coating, and a similar method.

Examples of the dry coating method include vacuum deposition,sputtering, CVD and a similar method. The specific examples of thevacuum deposition include resistance heating, electron beam,high-frequency heating, ion beam, and a similar method. The specificexamples of the CVD method include plasma-CVD, optical CVD, thermal CVDand a similar method.

Additionally, coating can be performed by an atmospheric pressure plasmamethod.

When the wet coating method is used, the surface-treating agent of thepresent invention is diluted with a solvent, and then it is applied tothe surface of the base material. In view of stability of thefluorine-containing compound or the composition and volatile property ofthe solvent, the following solvents are preferably used: an aliphaticperfluorohydrocarbon having 5-12 carbon atoms (for example,perfluorohexane, perfluoromethylcyclohexane andperfluoro-1,3-dimethylcyclohexane); an aromatic polyfluorohydrocarbon(for example, bis(trifluoromethyl)benzene); an aliphaticpolyfluorohydrocarbon; a hydrofluoroether (HFE) (for example, an alkylperfluoroalkyl ether such as perfluoropropyl methyl ether (C₃F₇OCH₃),perfluorobutyl methyl ether (C₄F₉OCH₃), perfluorobutyl ethyl ether(C₄F₉OC₂H₅), and perfluorohexyl methyl ether (C₂F₅CF(OCH₃)C₃F₇) (theperfluoroalkyl group and the alkyl group may be liner or branched)), andthe like. These solvents may be used alone or as a mixture of 2 or morecompound. Among them, the hydrofluoroether is preferable, perfluorobutylmethyl ether (C₄F₉OCH₃) and/or perfluorobutyl ethyl ether (C₄F₉OC₂H₅)are particularly preferable.

After forming the film of the surface treatment agent by using the abovemethod, if necessary, post-treatment may be performed. Examples of thepost-treatment include, but are not particularly limited to, for exampleheating to 40-150° C., for example 60-100° C.

As described above, the surface-treating layer derived from the film ofthe surface-treating agent of the present invention is formed on thesurface of the base material to produce the article of the presentinvention.

Therefore, the surface treatment agent can be suitably used to form thesurface-treating layer on an outermost layer of an optical material.Examples of the optical material include preferably a variety of opticalmaterials: for example, displays such as a cathode ray tube (CRT; forexample, TV, personal computer monitor), a liquid crystal display, aplasma display, an organic EL display, an inorganic thin-film EL dotmatrix display, a rear projection display, a vacuum fluorescent display(VFD), a field emission display (FED; Field Emission Display), or aprotective plate of such displays, or that in which these displays andprotective plates have been subjected to antireflection treatment ontheir surface.

The article having the surface-treating layer obtained according to thepresent invention is not specifically limited to, but may be an opticalmember. Examples of the optical member include the followings: lens ofglasses, or the like; a front surface protective plate, anantireflection plate, a polarizing plate, or an anti-glare plate on adisplay such as PDP and LCD; a touch panel sheet of an instrument suchas a mobile phone or a personal digital assistance; a disk surface of anoptical disk such as a Blu-ray disk, a DVD disk, a CD-R or MO; anoptical fiber, and the like.

The thickness of the surface-treating layer is not specifically limited.For the optical member, the thickness of the surface-treating layer iswithin the range of 0.1-30 μm, preferably 0.5-20 μm, in view of opticalperformance, friction durability and antifouling property.

The surface-treating layer formed from the surface treatment agent ofthe present invention may have water-repellency, oil-repellency,antifouling property, surface slip property, water-proof property and/orhigh friction durability, thus may be suitably used as a functional thinfilm.

In one embodiment, the composition of the present invention is amodifying agent.

The modifying agent of the present invention comprises at least onepolymer having a group of the formula (Ib) at the terminal of the mainchain of the present invention described above and can modify solubilityin an organic solvent of a base material, for example, a polymermaterial.

Thought, the modifying agent of the present invention can exhibit afunction even when it contains only the polymer having a group of theformula (Ib) at the terminal of the main chain of the present invention,the modifying agent may further contain a solvent.

Examples of the solvents described above are not particularly limited aslong as it can dissolve the polymer having a group of the formula (Ib)at the terminal of the main chain of the present invention or can becompatible with the polymer having a group of the formula (Ib) at theterminal of the main chain of the present invention, and include, forexample, a fluorine-containing aliphatic or aromatic hydrocarbons, andthe like, in particular, perfluorohexane, bis(trifluoromethyl)benzene,and the like.

The modifying agent of the present invention can be suitably applied toany base material (for example, polymer material) as long as it hasreactivity with a nitrileoxide group.

Examples of the polymer materials include, but are not particularlylimited to, PAN (polyacrylonitrile) having a nitrile group (C≡N) in themolecular, NR (natural rubber) having a carbon-carbon double bond (C═C)in the molecular, EPDM (ethylene-propylene-diene copolymer rubber),polynorbornene, NBR (nitrile rubber) having a nitrile group and acarbon-carbon double bond in the molecular, and the like.

Modifying treatment using the modifying agent of the present inventioncan be carried out by contacting the polymer having a group of theformula (Ib) at the terminal of the main chain of the present inventionwith a polymer material in an organic solvent or without a solvent,although the present invention is not particularly limited thereto.

The solvents described above are, but not particularly limited to,preferably a solvent in which both the polymer material and the polymerhaving a group of the formula (Ib) at the terminal of the main chain ofthe present invention are easily dissolved. Specifically, it includeschloroform, DMF (N,N-dimethylformamide), and the like.

When the treatment is carried out in the absence of a solvent, thetreatment may be carried out under air or an atmosphere where inert gasis filled.

Examples of the inert gases include, but are not particularly limitedto, argon, nitrogen, and the like.

When the modifying treatment is carried out in the absence of a solvent,the modifying treatment is preferably carried out in a kneader.

Examples of the kneader include, but are not particularly limited to,kneaders such as a biaxial kneader, an internal mixer, and a Banburymixer, or extruders such as a twin-screw extruder, a single screwextruder and a multi-screw extruder, and the like.

A temperature of the modifying treatment is not particularly limited aslong as the polymer having a group of the formula (Ib) at the terminalof the main chain of the present invention can be reacted with thepolymer material at the temperature, is preferably 0-150° C. since thechemical reaction is facilitated at higher temperature, on the otherhand, a management of the manufacturing process is easy if a temperaturecontrol such as heating is not performed. Furthermore, the temperatureis more preferably 20-100° C. when the polymer material is a polymerwhich has at least carbon-carbon double bond as a multiple bond, forexample, NBR, NR, EPDM, or the like, and the temperature is morepreferably 60-150° C. when the polymer material is a polymer which hasonly carbon-carbon triple bond as a multiple bond, for example, PAN orthe like.

Additionally, the present invention provides a modified material, forexample a modified polymer material, treated with the modifying agentdescribed above.

In the modified polymer material treated with the modifying agent of thepresent invention, its solubility in various organic solvent is varied,and its resistance to sunlight and ozone is improved, as a result ofwhich its durability is improved.

In one embodiment, the composition of the present invention is a fillermodifier.

The filler modifier of the present invention comprises at least onepolymer having a group of the formula (Ib) at the terminal of the mainchain of the present invention.

Examples of the filler to which the filler modifier of the presentinvention is applied include a filler having a group reactive with anitrileoxide group on its surface, for example, but are not particularlylimited to, silica particles, alumina, titanium oxide, barium oxide andcalcium oxide in which a group having an unsaturated bond such as avinyl group, an allyl group, and a nitrile group is introduced on itssurface.

The method for introducing the group having an unsaturated bond such asa vinyl group, an allyl group, and a nitrile group to the surface ofsilica particles is well known by those skilled in the art. For example,introduction of a vinyl group to the surface of the silica particles canbe carried out by treating the silica particles with a vinyl-basedsilane coupling agent (e.g. vinylethoxysilane, or the like).

The modification treatment using the filler modifier can be carried outsimply by mixing the filler modifier with the filler. The modificationtreatment is carried out in a solvent.

Examples of the solvent are not particularly limited as long as it isinert to the compound of the present invention and the filler, andinclude, for example, water, an aliphatic perfluorohydrocarbon having5-12 carbon atoms (for example, perfluorohexane,perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); anaromatic polyfluorohydrocarbon (for example,bis(trifluoromethyl)benzene); an aliphatic polyfluorohydrocarbon; ahydrofluoroether (HFE) (for example, an alkyl perfluoroalkyl ether suchas perfluoropropyl methyl ether (C₃F₇OCH₃), perfluorobutyl methyl ether(C₄F₉OCH₃), perfluorobutyl ethyl ether (C₄F₉OC₂H₅), and perfluorohexylmethyl ether (C₂F₅CF(OCH₃)C₃F₇) (the perfluoroalkyl group and the alkylgroup may be liner or branched)), and the like.

The present invention also provides a filler which is treated with thefiller modifier, for example silica particles.

The filler which is treated with the filler modifier has effects, forexample when it is used as a filler for a fluorine rubber, a perfluororubber or a fluororesin, dispersibility is improved or a reaction of areactive group on the surface of the filler (for example, SiO₂ insilica) with a fluorine-containing polymer can be suppressed incomparison with an untreated filler.

In one embodiment, the composition of the present invention is areactive compatibilizing agent.

The reactive compatibilizing agent of the present invention comprisesany of at least one polymer having a monomer unit of the formula (Ia),at least one polymer having a monomer unit of the formula (IIa), atleast one polymer having a group of the formula (Ib) at the terminal, ofthe present invention, and can improve compatibility between two or morematerials (compounds). For example, the reactive compatibilizing agentof the present invention can improve compatibility (i) between a(non-fluorine-containing) general-purpose polymer reactive with anitrileoxide group and a fluorine-containing polymer or (ii) between ageneral-purpose polymer and a fluorine-containing polymer reactive witha nitrileoxide group.

Since it is possible to introduce various groups into the polymer of thepresent invention depending to a compound to be compatibilized, thereactive compatibilizing agent of the present invention is able tocompatibilize various compounds. For example, for compatibilizing (i)between a (non-fluorine-containing) general-purpose polymer reactivewith a nitrileoxide group and a fluorine-containing polymer, thereactive compatibilizing agent of the present invention is able to besuitably used in any combinations as long as these are a combination ofa compound which has a fluorine-containing group and is reactive with anitrileoxide group and a fluorine-containing compound. Forcompatibilizing (ii) between a fluorine-containing polymer reactive witha nitrileoxide group and a general-purpose polymer, the reactivecompatibilizing agent of the present invention is able to be suitablyused in any combinations as long as these are a combination of afluorine-containing polymer which has a non-fluorine-containing groupand is reactive with a nitrileoxide group and a general-purpose polymer.In addition, a combination of compounds to be compatibilized (becomplexed) may be a combination of three or more compounds, for example,one compound reactive with a nitrileoxide group and twofluorine-containing compounds.

The compound having reactivity with the nitrileoxide group is notlimited as long as the compound is a polymer having a moiety reactivewith the nitrileoxide group (preferably, C═C, C≡N) in the moleculedescribed above. The moiety reactive with the nitrileoxide group may bein the backbone itself of the polymer described below, or when themoiety is absent, a substituent having moiety reactive with thenitrileoxide group may be introduced into the polymer.

Examples of the general-purpose polymers include, for example, polymerscontaining an aromatic ring in the main chain or the side chain(polystyrene, polyamide, polyimide, polycarbonate, polyphenylene ether,polyalkylene terephthalates, polysulfones, polyphenylene sulfide,polyaryl ether ketone, etc.), polypropylene, polyethylene etc., ornatural rubber, NBR (nitrile rubber), EPDM (ethylene-propylene-dienecopolymer rubber), PAN (polyacrylonitrile), polynorbornene,H₂C═C(R)—(CH₂—CHR)_(n)—CH₂—CR═CH₂ (wherein R is each independently ahydrogen atom, a methyl group, an ethyl group or an isobutyl group, andn is an integer from 10 to 1000), and the like.

Examples of the fluorine-containing compound include, but are notparticularly limited to, a fluororesin, a fluorine rubber, and the like.

Examples of the fluororesin include a non-melt processable fluororesin,for example, polytetrafluoroethylene (PTFE), and a melt processablefluororesin, and the like.

The PTFE may be a homopolymer of tetrafluoroethylene (TFE), or amodified polytetrafluoroethylene (modified PTFE). In the presentspecification, “modified PTFE” means a polymer obtained byco-polymerizing TFE with a co-monomer in such a small amount as not toprovide melt processability to the resulting copolymer. Examples of thesmall amount of co-monomer include, but are not limited to, for example,hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE),trifluoroethylene (TrFE), a perfluoro(alkyl vinyl ether) (PAVE), aperfluoro(alkoxyalkyl vinyl ether), a (perfluoroalkyl)ethylene, and thelike. The small amount of co-monomer can be used alone or two or more.

Examples of the PAVE include perfluoro(methylvinyl ether),perfluoro(ethylvinyl ether), perfluoro(propylvinyl ether), and the like.

A ratio of the small amount of co-monomer added to the modified PTFE is,when PAVE, a perfluoro(alkoxyalkyl vinyl ether), or the like is used,usually 0.001-1% by mass with respect to the total mass of TFE and thesmall amount of copolymer, but it is difficult depending on the type.

Examples of the melt processable fluororesin include atetrafluoroethylene (TFE)/hexafluoropropylene (HFP) copolymer, aTFE/HFP/perfluoro(alkyl vinyl ether) (PAVE) copolymer, a TFE/PAVEcopolymer (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer(PFA) and a tetrafluoroethylene-perfluoro methyl vinyl ether copolymer(MFA)), an ethylene (Et)/TFE copolymer, an Et/TFE/HFP copolymer,polychlorotrifluoroethylene (PCTFE), a chlorotrifluoroethylene(CTFE)/TFE copolymer, an Et/CTFE copolymer, a TFE/vinylidene fluoride(VDF) copolymer, a VDF/HFP/TFE copolymer, a VDF/HFP copolymer, and thelike.

Examples of the fluororesin further include a hydroxyl group containingand fluorine containing copolymer containing a fluoroolefin unit and ahydroxyl group-containing radical polymerizable unsaturated monomerunit.

Examples of the fluoroolefin unit include one or more of atetrafluoroethylene (TFE) unit, a chlorotrifluoroethylene (CTFE) unit, avinyl fluoride (VF) unit, a vinylidene fluoride (VDF) unit, ahexafluoropropylene (HFP) unit, a trifluoroethylene (TrFE) unit, aperfluoro(alkyl vinyl ether) (PAVE) unit. Examples of the PAVE unitinclude a perfluoromethyl vinyl ether unit and a perfluoropropylvinylether unit.

Examples of the combination of two or more units comprising the TFE unitinclude a TFE/HFP unit, a TFE/PAVE unit, a TFE/ethylene unit, aTFE/vinyl ether unit, a TFE/vinyl ester unit, a TFE/vinyl ester/vinylether unit, a TFE/vinyl ether/allyl ether unit, and the like. Amongthem, in view of readily mixing with an ethylenically unsaturatedgroup-containing monomer, the TFE/ethylene unit, the TFE/vinyl etherunit, the TFE/vinyl ester unit, the TFE/vinyl ester/vinyl ether unit,the TFE/vinyl ether/allyl ether unit, or the like is preferable.

Examples of the combination of two or more units comprising the CTFEunit include a CTFE/HFP unit, a CTFE/PAVE unit, a CTFE/ethylene unit, aCTFE/vinyl ether unit, a CTFE/vinyl ester unit, a CTFE/vinyl ester/vinylether unit, a CTFE/vinyl ether/allyl ether unit, and the like. Amongthem, in view of readily mixing with an ethylenically unsaturatedgroup-containing monomer, the CTFE/ethylene unit, the CTFE/vinyl etherunit, the CTFE/vinyl ester unit, the CTFE/vinyl ester/vinyl ether unit,the CTFE/vinyl ether/allyl ether unit, or the like is preferable.

Examples of the combination of two or more units comprising the HFP unitinclude a CTFE/HFP unit, a TFE/HFP unit, a HFP/vinyl ether unit, aHFP/vinyl ester unit, a HFP/vinyl ester/vinyl ether unit, a HFP/vinylether/allyl ether unit, and the like. Among them, in view of readilymixing with an ethylenically unsaturated group-containing monomer, theHFP/vinyl ether unit, the HFP/vinyl ester unit, the HFP/vinylester/vinyl ether unit, the HFP/vinyl ether/allyl ether unit, or thelike is preferable.

Examples of the combination of two or more units comprising the VDF unitinclude a VDF/TFE unit, a VDF/HFP unit, a VDF/TFE/HFP unit, a VDF/CTFEunit, a VDF/TFE/PAVE unit, a VDF/CTFE/TFE unit, a VDF/CTFE/HFP unit, andthe like. Among them, in view of readily mixing with an ethylenicallyunsaturated group-containing monomer, it is preferable that the VDF unitis contained in the polymer at 50 mol % or more.

Specific examples of the hydroxyl group-containing radical polymerizableunsaturated monomer unit of the hydroxyl group containing and fluorinecontaining copolymer include, for example, a hydroxyalkyl vinyl ether ora hydroxyalkyl allyl ether of the formula:

wherein R¹ is —OR² or —CH₂OR² (wherein R² is an alkyl group having ahydroxyl group). R² is, for example, a group which 1-3 hydroxyl groups,preferably one hydroxyl group is linked to a straight or branched alkylgroup having 1-8 carbon atoms. Examples of them include, for example, a2-hydroxyethylvinyl ether unit, a 3-hydroxypropylvinyl ether unit, a2-hydroxypropylvinyl ether unit, a 2-hydroxy-2-methylpropylvinyl etherunit, a 4-hydroxybutylvinyl ether unit, a 4-hydroxy-2-methylbutylvinylether unit, a 5-hydroxypentylvinyl ether unit, 6-hydroxyhexylvinyl etherunit, a 2-hydroxyethylallyl ether unit, a 4-hydroxybutylallyl etherunit, an ethylene glycol monoallyl ether unit, a diethylene glycolmonoallyl ether unit, a triethylene glycol monoallyl ether unit, aglycerin monoallyl ether unit, and the like. Among them, a hydroxyalkylvinyl ether having 1-3 carbon atoms is particularly preferable, and a4-hydroxybutylvinyl ether unit or a 2-hydroxyethylvinyl ether unit ismore preferable in view of easy polymerization.

The hydroxyl group containing and fluorine containing copolymer mayfurther comprise a hydroxyl-free and fluorine-free vinyl ether unitand/or a fluorine-free vinyl ester unit

Specific examples of the hydroxyl group-free and fluorine-free vinylether unit and/or the fluorine-free vinyl ester unit in the hydroxylgroup containing and fluorine containing copolymer include, for example,an alkyl vinyl ether or an alkyl allyl ether of the formula:

wherein R³ is —OR⁴, —COOR⁴ or —OCOR⁴ (wherein R⁴ is an alkyl group). R⁴is, for example, a straight, branched or cyclic alkyl group having 1-8carbon atoms. As examples of them, for example, a cyclohexylvinyl etherunit, a methylvinyl ether unit, an ethylvinyl ether unit, a propylvinylether unit, an n-butylvinyl ether unit, an isobutylvinyl ether unit, avinyl acetate unit, a vinyl propionate unit, a vinyl butyrate unit, avinyl isobutyrate unit, a vinyl pivalate unit, a vinyl caproate unit, avinyl versatate unit, a vinyl laurate unit, a vinyl stearate unit or avinyl cyclohexyl carboxylate unit is preferable. Furthermore, in view ofexcellent weather resistance, solubility and low-cost, vinyl versatate,vinyl laurate, vinyl stearate, a vinyl cyclohexyl carboxylate, or vinylacetate is preferable. Among them, in view of chemical resistance, anon-aromatic vinyl carboxylate ester, in particular a carboxylic acidvinyl ester having 6 or more carbon atoms in carboxylic acid ispreferable, and a carboxylic acid vinyl ester having 9 or more carbonatoms in carboxylic acid is more preferable. The upper limit of carbonatoms of carboxylic acid in the carboxylic acid vinyl ester ispreferably 20 or less, more preferably 15 or more. As a specificexample, vinyl versatate is most preferably.

The hydroxyl group containing and fluorine containing copolymer maycontain a carboxyl group-containing monomer unit.

The carboxyl group-containing monomer unit contains a carboxyl group anddoes not contain a hydroxyl group and an aromatic group, and in thispoint, it differs from the other units.

Examples of the carboxyl group-containing monomer unit include, forexample, a carboxyl group-containing vinyl monomer of the formula:

wherein R³, R⁴ and R⁵ is same or different, and are a hydrogen atom, analkyl group, a carboxyl group or an ester group, and n is 0 or 1

or the formula:

CH₂═CHCH₂_(n)O—R⁶OCO_(m)R⁷COOH

wherein R⁶ and R⁷ are same or different, and are a saturated orunsaturated straight or cyclic alkyl group, n is 0 or 1, and m is 0 or1.

Specific examples of the carboxyl group-containing monomer unit include,for example, one or more selected from acrylic acid, methacrylic acid,vinyl acetate, crotonic acid, cinnamic acid, 3-allyloxy propionic acid,itaconic acid, itaconic acid monoester, maleic acid, maleic acidmonoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinylphthalate and vinyl pyromellitate. Among them, crotonic acid, itaconicacid, maleic acid, maleic acid monoester, fumaric acid, fumaric acidmonoester, and 3-allyloxy propionic acid which have lowhomopolymerizality are preferable.

The lower limit of the ratio of carboxyl group-containing monomer unitis 0.1 mol %, preferably 0.4 mol %, and the upper limit is 2.0 mol %,preferably 1.5 mol %.

Specific examples of the hydroxyl group containing and fluorinecontaining copolymer include, for example, following compounds:

(wherein the formula, the ratio by mole of a, b, and c is a:b:c=40 to60:3 to 15:5 to 45);

(wherein the formula, the ratio by mole of a, b, and c is a:b:c=40 to60:3 to 15:5 to 45:5 to 45);

(wherein the formula, the ratio by mole of a, b, c and d is a:b:c:d=40to 60:3 to 15:5 to 45:5 to 45);

(wherein the formula, the ratio by mole of a, b, c and d is a:b:c:d=40to 60:3 to 15:5 to 45:5 to 45, and i-Bu represents an isobutyl group);tetrafluoroethylene/vinyl versatate/hydroxybutyl vinyl ether;tetrafluoroethylene/vinyl versatate/hydroxyethyl vinyl ether/tert-butylvinyl benzoate; tetrafluoroethylene/vinyl versatate/hydroxybutyl vinylether/crotonic acid; and tetrafluoroethylene/vinylversatate/hydroxyethyl vinyl ether/vinyl benzoate/crotonic acid.

Examples of the fluorine rubber include a non-perfluoro fluorine rubberand a perfluoro fluorine rubber.

Examples of the non-perfluoro fluorine rubber include a vinylidenefluoride (VDF) fluorine rubber, tetrafluoroethylene (TFE)/propylene (Pr)fluorine rubber, tetrafluoroethylene (TFE)/propylene/vinylidene fluoride(VDF) fluorine rubber, ethylene/hexafluoropropylene (HFP) fluorinerubber, ethylene/hexafluoropropylene (HFP)/vinylidene fluoride (VdF)fluorine rubber, ethylene/hexafluoropropylene (HFP)/tetrafluoroethylene(TFE) fluorine rubber, fluorosilicone fluorine rubber andfluorophosphazene fluorine rubber. They can be used alone or can be usedin arbitrary combinations, as long as the effects of the presentinvention are not lost. Among them, a vinylidene fluoride fluorinerubber and a tetrafluoroethylene/propylene fluorine rubber arepreferable.

The vinylidene fluoride fluorine rubber means a fluorine-containingelastomeric copolymer comprising 45 to 85 mol % of vinylidene fluorideand 55 to 15 mol % of at least one other monomer copolymerizable withvinylidene fluoride. It is preferably referred to fluorine-containingcopolymer comprising 50 to 80 mol % of vinylidene fluoride and 50 to 20mol % of at least one monomer copolymerizable with vinylidene fluoride.

Examples of the at least one other monomer copolymerizable withvinylidene fluoride include, for example, fluorine-containing monomerssuch as tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE),trifluoroethylene, hexafluoropropylene (HFP), trifluoropropylene,tetrafluoropropylene, pentafluoropropylene, trifluorobutene,tetrafluoroisobutene, perfluoro(alkyl vinyl ether) (PAVE), vinylfluoride, and the like, and fluorine-free monomers such as ethylene,propylene, and alkyl vinyl ether. They can be used alone or inarbitrarily combinations. Among them, tetrafluoroethylene,hexafluoropropylene, and perfluoro (alkyl vinyl ether) are preferable.

In this case, examples of the perfluoro(alkyl vinyl ether) include, forexample, perfluoro(methylvinyl ether), perfluoro(propylvinyl ether), andthe like. They can be used alone or in arbitrary combinations, as longas the effects of the present invention are not lost.

Examples of the vinylidene fluoride fluorine rubber include a VDF-HFPrubber, a VDF-HFP-TFE rubber, a VDF-CTFE rubber, a VDF-CTFE-TFE rubber,and the like.

The tetrafluoroethylene/propylene fluorine rubber means afluorine-containing elastomer copolymer comprising 45 to 70 mol % oftetrafluoroethylene, 55 to 30 mol % of propylene, and 0 to 5 mol % of amonomer providing a cross-linking site.

Examples of the monomer providing a cross-linking site include, forexample, iodine-containing monomers such asperfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene) andperfluoro(5-iodo-3-oxa-1-pentene) described in JP 05-63482 B and JP07-316234 A, bromine-containing monomers described in JP 04-505341 A,cyano group-containing monomers, carboxyl group-containing monomers andalkoxycarbonyl group-containing monomers described in JP 04-505345 A andJP 05-500070 A.

Examples of the perfluoro fluorine rubber include a perfluoro rubbercontaining TFE, for example, a fluorine-containing elastomer copolymerconsisting of TFE/perfluoro(alkyl vinyl ether) (PAVE)/a monomerproviding a cross-linking site. The composition is preferably 45 to90/10 to 50/0 to 5 (mol %), more preferably, 45 to 80/20 to 50/0 to 5,further preferably, 53 to 70/30 to 45/0 to 2. If the composition is outof this range, property as a rubber elastomer is tend to be lost andbecome property close to a resin property.

In this case, examples of the PAVE include, for example,perfluoro(methylvinyl ether) (PMVE), perfluoro(propylvinyl ether)(PPVE), and the like. They can be used alone or in arbitrarycombinations, as long as the effects of the present invention are notlost.

Examples of the monomer providing a cross-linking site include, forexample, an iodine-containing monomer of the following formula:

CX₂═CX—R_(f)CHRI

wherein X is H, F or CH₃, R_(f) is a fluoroalkylene group, aperfluoroalkylene group, a fluoropolyoxyalkylene group or aperfluoropolyoxyalkylene group, and R is H or CH₃, and a monomer of thefollowing formula:

CF₂═CFO(CF₂CF(CF₃))_(m)—O—(CF₂)_(n)—Y

wherein m is an integer of 0-5, n is an integer of 1-3, Y is a nitrilegroup, a carboxyl group, an alkoxycarbonyl group or a bromine atom).They can be used alone or in arbitrary combinations, as long as theeffects of the present invention are not lost. The iodine atom, thenitrile group, the carboxyl group, the alkoxycarbonyl group, and thebromine atom function as the cross-linking site.

Specific examples of the perfluoro fluorine rubber include a fluorinerubber and the like described in WO 97/24381, JP 61-57324 B, JP 04-81608B, and JP 05-13961 B.

Examples of the other fluorine-containing polymer include homopolymersuch as PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride).

The reactive compatibilizing agent of the present invention can exertits function simply by mixing the reactive compatibilizing agentcontaining the compound of the present invention with the compoundreactive with a nitrileoxide group and the fluorine containing compoundin a step of mixing the compound reactive with a nitrileoxide group andthe fluorine containing compound under an atmosphere pressure in amixing equipment (a kneader, a brabender, an extruder, etc.). In thismixing step, the compound of the present invention click-reacts with areactive site of the compound reactive with a nitrileoxide group,thereby a fluorine-containing group can be introduced to the compoundreactive with a nitrileoxide group. This introduced fluorine-containinggroup has an affinity for the fluorine-containing compound, therebyenabling compatibilization (complexation) of the both compounds.

The above mixing step is usually carried out at a temperature at whichthe compound reactive with a nitrileoxide group and thefluorine-containing compound melts, for example, about 150-250° C. Forexample, when NBR as the compound reactive with a nitrileoxide group isused, and PVDF as the fluorine-containing compound is used, the step iscarried out at about 170° C. or more, for example, about 180-210° C.Since the compound of the present invention has a high thermalstability, such treatment at the high temperature can be carried out.

The above mixing step can be carried out usually without a solvent,additives, etc. However, the solvent or additives may be added dependingon a purpose, for example in order to accelerate the reaction. Thoseskilled in the art can select the solvent and the additives depending ona purpose.

Examples of a conventional general compatibilizing agent are a blockpolymer and a graft polymer which have both backbones of two componentsto be complexed. The compound of the present invention is advantageousin that the preparation is easy in comparison with the conventionalpolymer. In addition, the reactive compatibilizing agent of the presentinvention has an advantage in that it can compatibilize components to becompatibilized simply by mixing the reactive compatibilizing agent withthe mixture of the components.

In addition, the present invention provides a composite of two or morecompounds treated with the reactive compatibilizing agent of the presentinvention.

In one embodiment, the composition of the present invention is a fibertreatment agent.

The fiber treatment agent of the present invention contains any of atleast one polymer having a monomer unit of the formula (Ia), at leastone polymer having a monomer unit of the formula (IIa), at least onepolymer having a group of the formula (Ib) at the terminal, of thepresent invention, and can improve water-repellency and oil-repellencyof a fiber having a group reactive with a nitrileoxide group, forexample, an acrylate fiber.

The fiber treatment agent of the present invention can be suitably usedfor any fiber as long as it has the group reactive with a nitrileoxidegroup.

Examples of the fiber include an acrylate fiber, or a polyester fiber ora polyvinyl alcohol fiber obtained by copolymerizing a monomer having anitrile group in its side chain. In addition, even a fiber having nogroup reactive with a nitrileoxide group become to be able to be treatedwith the fiber treatment agent of the present invention by introducingthe group reactive with a nitrileoxide group thereto. For example, apolyester fiber or a polyvinyl alcohol fiber obtained by copolymerizinga monomer having a hydroxyl group or an amino group in its side chainbecome to be able to be treated with the fiber treatment agent of thepresent invention by dehydration-condensation with a carbonic acid orsulfonic acid compound reactive with a nitrileoxide group.

The fiber treatment agent of the present invention may contain,additives, for example, an emulsifying agent (polyethylene glycol-based,cationic, ammonium, nonionic, anionic), an antifoaming agent, a wettingagent, a paraffin hydrocarbon, and the like in addition to any of atleast one polymer having a monomer unit of the formula (Ia), at leastone polymer having a monomer unit of the formula (IIa), at least onepolymer having a group of the formula (Ib) at the terminal of thepresent invention.

The fiber treatment agent of the present invention may be diluted with asolvent before being applied to the fiber. Examples of the solventinclude, for example, an aliphatic perfluorohydrocarbon having 5-12carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexaneand perfluoro-1,3-dimethylcyclohexane); an aromaticpolyfluorohydrocarbon (for example, bis(trifluoromethyl)benzene); analiphatic polyfluorohydrocarbon; a hydrofluoroether (HFE) (for example,an alkyl perfluoroalkyl ether such as perfluoropropyl methyl ether(C₃F₇OCH₃), perfluorobutyl methyl ether (C₄F₉OCH₃), perfluorobutyl ethylether (C₄F₉OC₂H₅), and perfluorohexyl methyl ether (C₂F₅CF(OCH₃)C₃F₇)(the perfluoroalkyl group and the alkyl group may be liner orbranched)), other fluorine solvents, hydrocarbon solvents such as amineral oil, alcohol, MIBK (methyl isobutyl ketone), glycol-basedsolvents (ethylene glycol, propylene glycol etc.), and the like.

A method for applying the fiber treatment agent of the present inventionto the fiber is not particularly limited as long as it can attach thedesired amount of the agent of the fiber to be treated, and variousmethods can be used. the fiber treatment method includes, be acontinuous method or a batch method.

As the continuous method, first, the fiber treatment agent is dilutedwith a solvent to prepare a treating liquid. Then, an object to betreated is continuously supplied to an impregnation apparatus filledwith the treating liquid to impregnate the object to be treated with thetreating liquid, and then unnecessary treating liquid is removed. Theimpregnation apparatus is not particularly limited, and is preferably apadder impregnation apparatus, a kiss roller impregnation apparatus, agravure coater impregnation apparatus, a spray impregnation apparatus, afoam impregnation apparatus, a coating impregnation apparatus or thelike, particularly preferably a padder impregnation apparatus. Then, anoperation of removing the solvent remaining in the object is carried outby using a dryer. The dryer is not particularly limited, and ispreferably an expansion dryer such as a tenter or a hot flue. Thiscontinuous method is employed preferably in a case where the object tobe treated is cloth such as woven cloth.

The batch method comprises a step of immersing the object to be treatedwith a treating liquid, and a step of removing the solvent remaining inthe treated object. The batch method is employed preferably in a casewhere the object to be treated is not cloth, such as a case where it isbulk fiber, top, sliver, hank, tow or thread, or in a case where it isnot suitable for the continuous method such as a case where it isknitted fabric. In the immersion step, it is preferred to use, forexample, a cotton dyeing machine, a cheese dyeing machine, a jet dyeingmachine, an industrial washing machine or a beam dyeing machine. Inoperation of removing the solvent, it is preferred to use a hot airdryer such as a cheese dryer, a beam dryer or a tumble dryer, or amicrowave dryer

The treated object to which the fiber treatment agent of the presentinvention is attached is preferably subjected to a dry heat treatment.When the dry heat treatment is carried out, active ingredients in thefiber treatment agent of the present invention will more firmly attachto the object to be treated. The temperature for the dry heat treatmentis preferably from 120 to 180° C., more preferably from 160 to 180° C.The dry heat treatment time is preferably from 10 seconds to 3 minutes,more preferably from 1 to 2 minutes. The method of the dry heattreatment is not particularly limited, and it is preferred to use atenter in a case where the object to be treated is cloth.

In addition, the present invention provides a fiber treated with thefiber treatment agent.

The fiber treated with the fiber treatment agent of the presentinvention has improved water and oil repellency, weather resistanceand/or thermal resistance, or the like depending on the compound of thepresent invention used. In addition, since the compound of the presentinvention is chemically bonded to the fiber by click-reaction, the abovefunctions are less likely to deteriorate by friction, etc., and canmaintain the function for a long time.

In one embodiment, the composition of the present invention is across-linking agent.

The cross-linking agent of the present invention contains at least oneany of at least one polymer of the formula (Ia), at least one polymerhaving a monomer unit of the formula (IIa), at least one polymer havinga group of the formula (Ib) at the terminal, or the present invention,and can react with two functional groups reactive with a nitrileoxidegroup and cross-link between these functional groups. It is noted thatthe two functional groups may be present in same molecular or indifferent molecular, respectively.

Since any of at least one nitrileoxide polymer of the formula (Ia), atleast one polymer having a monomer unit of the formula (IIa), at leastone polymer having a group of the formula (Ib) at the terminal of thepresent invention has higher thermal resistance in comparison with theconventional aromatic multifunctional nitrileoxide, it can be used undera high temperature condition. Therefore, even when a compound to becross-linked is a polymer having a small amount of reaction sites (thatis, unsaturated sites) or a polymer whose back bone is rigid and haspoor molecular mobility, these compounds can be cross-linked bysubjecting these compounds a treatment under the high temperaturecondition. Specifically, even a polymer containing tetrafluoroethylenesuch as a base polymer of the fluorine rubber, a base polymer of theperfluoro rubber, or the like as a main ingredient can be suitablycross-linked.

The compound to be cross-linked is not particularly limited as long asit has a moiety reactive with a nitrileoxide group, and may be, forexample, a polymer having a moiety reactive with a nitrileoxide group,for example, a general-purpose rubber, a natural rubber, polynorbornene,a fluoropolymer (preferably, that obtained by polymerizing fluoroolefinsor fluorine-containing (metha)acrylates, particularly preferably, afluorine rubber).

Examples of the general-purpose rubber include, for example, NBR(nitrile rubber), EPDM (ethylene-propylene-diene copolymer rubber), PAN(polyacrylonitrile), H₂C═C(R)—(CH₂—CHR)_(n)—CH₂—CR═CH₂ (wherein R iseach independently a hydrogen atom, a methyl group, an ethyl group, oran isobutyl group, and n is an integer of 10-1000).

The natural rubber is a rubbery polymer naturally occurring in normal,and usually has a polyisoprene structure, although is not limitedthereto.

The fluorine-containing (meth) acrylates are a compound ofH₂C═C(X)—CO—O—Y, wherein X is a hydrogen atom, a methyl group, an ethylgroup, a trifluoromethyl group, a fluorine atom, or a chlorine atom, andY is a linear or branched alkyl group having at least one a fluorogroup, preferably an alkyl group comprising a skeleton of aperfluoroalkylene group or a perfluoroalkyl group, particularlypreferably, —CH₂ (CF₂)_(n)H, —CH₂CH₂ (CF₂)_(n)F.

The fluorine rubber may be either a non-perfluoro fluorine rubber or aperfluoro fluorine rubber, for example, and preferably has a structuralunit derived from at least one monomer selected from the groupconsisting of tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and aperfluoroethylenically unsaturated compound (for example,hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), and thelike) of the following formula (a):

CF₂═CF—Rf^(a)  (a)

wherein Rf^(a) represents —CF₃ or ORf^(b) wherein Rf^(b) represents aperfluoroalkyl group having 1-5 carbon atoms.

Examples of the non-perfluoro fluorine rubber include a vinylidenefluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE)/propylene (Pr)fluorine rubber, tetrafluoroethylene (TFE)/propylene (Pr)/vinylidenefluoride (VdF) fluorine rubber, ethylene (Et)/hexafluoropropylene (HFP)fluorine rubber, ethylene (Et)/hexafluoropropylene (HFP)/vinylidenefluoride (VdF) fluorine rubber, ethylene (Et)/hexafluoropropylene(HFP)/tetrafluoroethylene (TFE) fluorine rubber, fluorosilicone fluorinerubber and fluorophosphazene fluorine rubber. They can be used alone orin combinations. In addition, these fluorine rubbers may be a copolymerwith co-monomer.

The co-monomer is not particularly limited as long as it cancopolymerize with other monomer, and include, for example, TFE, HFP,PAVE, chlorotrifluoroethylene (CTFE), trifluoroethylene,trifluoropropylene, tetrafluoropropylene, pentafluoropropylene,trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinylfluoride, an iodine-containing and fluorine-containing vinyl ether,perfluorovinyl ether such as a fluorine-containing monomer of theformula (b):

CH₂═CFRf^(b)  (b)

wherein Rf^(b) is a straight or branched fluoroalkyl group having 1-12carbon atoms;a fluorine-containing monomer (c);

CF₂═CFOCF₂ORf^(c)  (c)

wherein Rf^(c) is a straight or branched perfluoroalkyl group having 1-6carbon atoms, a cyclic perfluoroalkyl group having 5-6 carbon atoms or astraight or branched perfluorooxyalkyl group having 1-3 oxygen atoms and2-6 carbon atoms;a fluorine-free monomer such as ethylene (Et), propylene (Pr), alkylvinyl ether; and, a reactive emulsifier. They can be used alone or incombination with two or more.

Examples of the copolymer include, but are not particularly limited to,for example, at least one copolymer selected from the group consistingof a VdF/HFP copolymer, a VdF/TFE/HFP copolymer, a VdF/CTFE copolymer, aVdF/CTFE/TFE copolymer, a VdF/PAVE copolymer, a VdF/TFE/PAVE copolymer,a VdF/HFP/PAVE copolymer, a VdF/HFP/TFE/PAVE copolymer, aVdF/TFE/propylene(Pr) copolymer, a VdF/ethylene(Et)/HFP copolymer and acopolymer of VdF/the fluorine-containing monomer (b) of the formula (b).

The reactive site with a nitrileoxide group in the fluorine rubber maybe derived from a monomer having the reactive site or may be introducedby modifying a fluorine rubber having no reactive site.

Examples of the monomer having a reactive site with a nitrileoxide groupinclude, for example, a bisolefin compound of the formula:

R²²R²³C═CR²⁴—Z—CR²⁵═CR²⁶R²⁷

wherein R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are same or difference, and areindependently represent a hydrogen atom or an alkyl group having 1-5carbon atoms; and

Z represents a straight or branched alkylene or an cycloalkylene grouphaving 1-18 carbon atoms which may have an oxygen atom and preferablyfluorinated at least partially, or a (per)fluoropolyoxyalkylene group.

Other examples of the monomer having a reactive site with a nitrileoxidegroup include an olefin compound having a nitrile group, for example, acompound of the formula:

R²⁸R²⁹C═CR³⁰—Z—CN

wherein R²⁸, R²⁹ and R³⁰ are same or different, and independentlyrepresent a hydrogen atom or an alkyl group having 1-5 carbon atoms; and

Z represents a straight or branched alkylene or an cycloalkylene grouphaving 1-18 carbon atoms which may have an oxygen atom and preferablyfluorinated at least partially or a (per)fluoropolyoxyalkylene group,representatively, CF₂═CFOCF₂CF(CF₃) OCF₂CF₂CN.

Another examples of the monomer having a reactive site with anitrileoxide group include acrylonitrile, 5-ethylidene-2-norbornene, anda styrene derivative having a nitrile group on the aromatic ring.

In one embodiment, the composition of the present invention can alsofunction as a filler.

The filler of the present invention comprise at least one polymerscomprising one or more monomer units of the formula (Ia), and at leastone polymers comprising a monomer unit of the formula (IIa) and a groupof the formula (Ib) at the terminal. Since the filler contains anitrileoxide group, the filler is filled while efficiently forming thebond with a material to be mixed.

The material to be mixed with the composition of the present inventionis not limited as long as it is a polymer material, and examples of thematerial include, for example, a fluorine-containing polymer such as afluorine resin, a fluorine rubber, or the like.

With respect to the function as a filler, the composition of the presentinvention may have a desired function by designing a structure of thecomposition depending on the purpose, and may have, for example, afunction to provide the material to be mixed with properties such asmechanical strength, antimicrobial, gas barrier property, conductivity,flame retardancy, weather resistance, water absorption property, or thelike.

Although the present invention is not limited to the below, for example,when a crosslinkable filler having a polyamide type structure is used asthe polymer of the formula (Ia), the mechanical strength of the materialto be mixed can be enhanced. The crosslinkable filler acts also as acrosslinking agent, and since the crosslinkable filler can form achemical bond with the material to be mixed, the crosslinkable fillerprovides the higher effect to increase than a usual filler which is notcrosslinkable. As mentioned above, when the polyamide structure havinghigh mechanical strength is used as a polymer of the formula (Ia), thepolymer can provide a mechanical reinforcing effect, in addition, byusing a polymer backbone having desired properties as the composition ofthe present invention, the desired properties can be provided to thematerial to be mixed. As noted above, the polymer represented by formula(Ia), in case of adopting the polyamide backbone having a highmechanical strength is mechanical reinforcing effect is obtained, thedesired as a composition of the present invention by employing a polymerbackbone having the characteristics, it is possible to impart desiredproperties to the kneading mating member.

The size of the filler is, but is not particularly limited to, usuallyabout 100 nm to 10 nm.

The shape of the filler may be, but is not particularly limited to, forexample, spherical, completely spherical, granular, fibrous, plate, orthe like.

Examples of a method of mixing the composition of the present inventionto the material includes, but are not particularly limited to, usually,the kneading by human power in a mortar, the kneading by using anapparatus such as a roll, a kneader, an extruder, and the kneading inthe apparatus providing a supercritical condition environment.

When the composition is mixed with the material, if necessary, apretreatment may be performed. The pretreatment provides, for example,the effect to facilitate dispersion of the particles, the effect ofpreventing aggregation, the effect of improving the workability, theeffect to increase the wettability to the material to which thecomposition is added.

In one embodiment, the composition of the present invention is used as araw material of a low-temperature property rubber.

The low-temperature property rubber can be produced by producing afluorine rubber or a perfluororubber by the composition of the presentinvention.

The fluorine rubber and the perfluororubber are not limited as long ashaving the reactivity with the nitrileoxide group, and include, forexample, the non-perfluoro fluorine rubber and the perfluoro fluorinerubber described above.

In the production of the low-temperature property rubber, thecomposition of the present invention is used as follows, although thepresent invention is not particularly limited thereto.

The compositions of the present invention is added and mixed at the sametiming as adding and mixing of a crosslinking agent and/or a fillerwhich is added as necessary in a kneading process (roll kneading,Banbury mixing, etc.) after preparing a base polymer of thefluorine-containing rubber by general polymerization. The base polymerin which the compound is sufficiently dispersed in this way is subjectedto the press (first vulcanization), and oven heating (secondvulcanization), as a result, clicks reaction of the compound of thepresent invention with unsaturated bonds in the fluorine-containingpolymer occurs, thereby obtaining the low temperature properties rubber.

The above process is usually performed in the absence of a solvent. Ifnecessary, for example, in order to improve the dispersibility of thecompound of the present invention, a solvent may be used. The solvent isappropriately selected depending on the type of the raw material to beused and the low-temperature property rubber of interest, for example,the solvent includes a fluorine-containing solvent.

Since an untreated fluorine-containing rubber generally has a skeletonin which the molecular backbone is rigid, the untreatedfluorine-containing rubber has insufficient molecular movement in a lowtemperature environment, as a result of which, sufficient elasticitycannot be obtained. However, by treating the fluorine-containing rubberwith the compound of the present invention, the elasticity in the lowtemperature environment can be increased while maintaining otherproperties such as chemical resistance and heat resistance. it can beimproved elasticity at low temperature environment. Although the presentinvention is not limited by theory, the reason for improving ofelasticity property in the low temperature environment by treating thefluorine-containing rubber with the compound of the present inventionmay be considered as follows. The compound of the present invention mayhave a group having high molecular mobility and a flexible skeleton as asubstituent, for example, a perfluoropolyalkylether group. By reactingthe compound with the moiety (for example, double bond, triple bond)reactive with the fluorine-containing rubber and grafting them, themolecular mobility of fluorine rubber itself is increased, as a result,sufficient elasticity can be achieved in the low temperatureenvironment. In addition, by applying a group having excellent chemicalresistance and heat resistance as the substituent which the compound ofthe present invention, for example by applying a perfluoroalkylethergroup, the chemical resistance and heat resistance of thefluorine-containing rubber can be maintained.

The present invention provides a low temperature property rubberprepared by using the composition of the present invention.

In one embodiment, the composition of the present invention is used as araw material of a liquid rubber.

The composition of the present invention used as the raw material of aliquid rubber (hereinafter, referred to as “Liquid rubber rawcomposition 1”) contains at least one polymer having a group of theformula (Ib) at the terminal of the main chain of the present invention.

By mixing Liquid rubber raw composition 1 with a composition containinga compound having an unsaturated bond (hereinafter, “Liquid rubber rawcomposition 2”), a click-reaction between the nitrileoxide groupcontained in the compound of the present invention and the unsaturatedbond contained in the compound in Liquid rubber raw composition 2 occursto produce a gel-like production (that is, a liquid rubber).

Examples of the compound having an unsaturated bond in contained inLiquid rubber raw composition 2 include, but are not limited to, one ormore compounds of the formula:

CH₂═CH—(X)_(a)—Rf²—(X)_(a)—CH═CH₂

wherein:

X is each independently —CH₂—, —CH₂O—, —CH₂OCH₂—, or —CH₂—NR¹—CO—;

Y is —CH₂—;

Rf¹ is a di-valent perfluoroalkylene group; and

a is each independently an integer of 0 or 1;

andone or more compounds of the formula:

Rf²—(X)_(a)—CH═CH₂

wherein:

X is each independently —CH₂—, —CH₂O—, —CH₂OCH₂— or —CH₂—NR¹—CO—;

Y is —CH₂—:

Rf² is a perfluoropolyalkyl group; and

a is each independently an integer of 0 or 1.

Specific examples of the compound having an unsaturated bond containedin Liquid rubber raw composition 2 include, for example, triallylisocyanurate (TAIC), triallyl trimellitate, diallyl phthalate, triallylphosphite, N,N-diallyl acrylamide, 1,6-vinyl dodecafluorohexane,bismaleimide, triallyl phosphate, and the like.

In the conventional producing of a liquid rubber, a metal catalyst suchas a platinum compound was essential. However, the present invention hasan advantage to be able to produce a liquid rubber simply by mixingLiquid rubber raw composition 1 and Liquid rubber raw composition 2. Byusing the composition of the present invention, a catalyst-free liquidrubber can be produced. For example, such liquid rubber can be suitablyused in the semiconductor manufacturing process on which the presence ofthe metal can adversely affect.

In the conventional producing of a liquid rubber, a curing reaction isperformed by hydrosililation, and a liquid rubber obtained by thismethod contains Si atom. This backbone containing Si atom has lowresistance against a fluorine active species (a fluorine gas, a fluorineplasma, a fluorine radical) and is not suitable for use in a step inwhich the active species is generated in the semiconductor manufacturingprocess. Since the liquid rubber obtained by using the composition ofthe present invention is produced without using a backbone containing Siatom, the liquid rubber containing no Si atom can be easily produced ifnecessary. In this point, the present invention is advantageous.

In addition, the present invention provides a liquid rubber produced byusing the composition of the present invention.

In one embodiment, the composition of the present invention is used as araw material of a thermosetting polymer material (a resin or a rubber).

The composition (hereinafter, also referred to as “a “thermosettingpolymer material raw material composition 1”) used as a thermosettingpolymer material contains any of at least one polymer of the formula(Ia), at least one polymer having a monomer unit of the formula (IIa),at least one polymer having a group of the formula (Ib) at the terminalof the present invention. In a preferable embodiment, the compound ofthe present invention used herein is a material having both a groupwhich is reactive with a nitrileoxide group under high temperature (forexample, C═C bond, C≡N bond, C≡C) and a nitrileoxide group in theskeleton.

The thermosetting polymer material raw material composition 1 may be acomposition comprising at least one material reactive with anitrileoxide group. The material having reactivity with the nitrileoxidegroup is not limited as long as the material is a polymer having amoiety reactive with the nitrileoxide group (preferably, C═C, C≡N). Themoiety reactive with the nitrileoxide group may be in the backboneitself of the polymer, or when the moiety is absent, a substituenthaving moiety reactive with the nitrileoxide group may be introducedinto the polymer.

The material having reactivity with the nitrileoxide group is notparticularly limited, and may be for example, a polymer having a moietyreactive with a nitrileoxide group, for example, a general-purposerubber, a natural rubber, polynorbornene, a fluoropolymer (preferably,that obtained by polymerizing fluoroolefins or fluorine-containing(metha)acrylates, particularly preferably, a fluorine rubber).

Examples of the general-purpose rubber include, for example, NBR(nitrile rubber), EPDM (ethylene-propylene-diene copolymer rubber), PAN(polyacrylonitrile), H₂C═C(R)—(CH₂—CHR)_(n)—CH₂—CR═CH₂ (wherein R iseach independently a hydrogen atom, a methyl group, an ethyl group, oran isobutyl group, and n is an integer of 10-1000).

The natural rubber is a rubbery polymer naturally occurring in normal,and usually has a polyisoprene structure, although is not limitedthereto.

The fluorine-containing (meth) acrylates are a compound ofH₂C═C(X)—CO—O—Y, wherein X is a hydrogen atom, a methyl group, an ethylgroup, a trifluoromethyl group, a fluorine atom, or a chlorine atom, andY is a linear or branched alkyl group having at least one a fluorogroup, preferably an alkyl group comprising a skeleton of aperfluoroalkylene group or a perfluoroalkyl group, particularlypreferably, —CH₂ (CF₂)_(n)H, —CH₂CH₂ (CF₂)_(n)F.

The fluorine rubber may be either a non-perfluoro fluorine rubber or aperfluoro fluorine rubber, for example, and preferably has a structuralunit derived from at least one monomer selected from the groupconsisting of tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and aperfluoroethylenically unsaturated compound (for example,hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), and thelike) of the following formula (a):

CF₂═CF—Rf^(a)  (a)

wherein Rf^(a) represents —CF₃ or ORf^(b) wherein Rf^(b) represents aperfluoroalkyl group having 1-5 carbon atoms.

Examples of the non-perfluoro fluorine rubber include a vinylidenefluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE)/propylene (Pr)fluorine rubber, tetrafluoroethylene (TFE)/propylene (Pr)/vinylidenefluoride (VdF) fluorine rubber, ethylene (Et)/hexafluoropropylene (HFP)fluorine rubber, ethylene (Et)/hexafluoropropylene (HFP)/vinylidenefluoride (VdF) fluorine rubber, ethylene (Et)/hexafluoropropylene(HFP)/tetrafluoroethylene (TFE) fluorine rubber, fluorosilicone fluorinerubber and fluorophosphazene fluorine rubber. They can be used alone orin combinations. In addition, these fluorine rubbers may be a copolymerwith co-monomer.

The co-monomer is not particularly limited as long as it cancopolymerize with other monomer, and include, for example, TFE, HFP,PAVE, chlorotrifluoroethylene (CTFE), trifluoroethylene,trifluoropropylene, tetrafluoropropylene, pentafluoropropylene,trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinylfluoride, an iodine-containing and fluorine-containing vinyl ether,perfluorovinyl ether such as a fluorine-containing monomer of theformula (b):

CH₂═CFRf^(b)  (b)

wherein Rf^(b) is a straight or branched fluoroalkyl group having 1-12carbon atoms;a fluorine-containing monomer (c);

CF₂═CFOCF₂ORf^(c)  (c)

wherein Rf^(c) is a straight or branched perfluoroalkyl group having 1-6carbon atoms, a cyclic perfluoroalkyl group having 5-6 carbon atoms or astraight or branched perfluorooxyalkyl group having 1-3 oxygen atoms and2-6 carbon atoms;a fluorine-free monomer such as ethylene (Et), propylene (Pr), alkylvinyl ether; and, a reactive emulsifier. They can be used alone or incombination with two or more.

Examples of the copolymer include, but are not particularly limited to,for example, at least one copolymer selected from the group consistingof a VdF/HFP copolymer, a VdF/TFE/HFP copolymer, a VdF/CTFE copolymer, aVdF/CTFE/TFE copolymer, a VdF/PAVE copolymer, a VdF/TFE/PAVE copolymer,a VdF/HFP/PAVE copolymer, a VdF/HFP/TFE/PAVE copolymer, aVdF/TFE/propylene(Pr) copolymer, a VdF/ethylene(Et)/HFP copolymer and acopolymer of VdF/the fluorine-containing monomer (b) of the formula (b).

The reactive site with a nitrileoxide group in the fluorine rubber maybe derived from a monomer having the reactive site or may be introducedby modifying a fluorine rubber having no reactive site.

Examples of the monomer having a reactive site with a nitrileoxide groupinclude, for example, a bisolefin compound of the formula:

R²²R²³C═CR²⁴—Z—CR²⁵═CR²⁶R²⁷

wherein R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are same or difference, and areindependently represent a hydrogen atom or an alkyl group having 1-5carbon atoms; and

Z represents a straight or branched alkylene or an cycloalkylene grouphaving 1-18 carbon atoms which may have an oxygen atom and preferablyfluorinated at least partially, or a (per)fluoropolyoxyalkylene group.

Other examples of the monomer having a reactive site with a nitrileoxidegroup include an olefin compound having a nitrile group, for example, acompound of the formula:

R²⁸R²⁹C═CR³⁰—Z—CN

wherein R²⁸, R²⁹ and R³⁰ are same or different, and independentlyrepresent a hydrogen atom or an alkyl group having 1-5 carbon atoms; and

Z represents a straight or branched alkylene or an cycloalkylene grouphaving 1-18 carbon atoms which may have an oxygen atom and preferablyfluorinated at least partially or a (per)fluoropolyoxyalkylene group,representatively, CF₂═CFOCF₂CF(CF₃) OCF₂CF₂CN.

Another examples of the monomer having a reactive site with anitrileoxide group include acrylonitrile, 5-ethylidene-2-norbornene, anda styrene derivative having a nitrile group on the aromatic ring.

The thermosetting polymer material raw material composition 1 can beused in the form containing a solvent, but can be usually used in theform containing no solvent.

The thermosetting polymer material raw material composition 1 causes acuring reaction by the increasing of the temperature. The environment ofthe curing reaction is not limited as long as the temperature can beincreased, and, the curing reaction is performed, for example, in amold, in a molding machine, in an oven, on a hot stage, in a mortar, orthe like.

The reaction temperature for causing a curing reaction is notparticularly limited, and is preferably a temperature higher than theglass transition temperature, more preferably the melting point of atleast one of the polymeric materials forming the thermosetting polymermaterial raw material composition 1.

The thermosetting polymer material raw material composition 1 can have adesign to provide a material having higher thermal and chemicalresistance than those of a conventional thermosetting polymer, asneeded. This is due to the fact that the nitrileoxide groups crosslinkwhile forming a chemically robust bond.

The curing reaction of the thermosetting polymer material raw materialcomposition 1 can be also caused in the presence of additives orreagents for advancing and facilitating the reaction, or can be alsocaused in the absence of the additives or reagents.

Hereinbefore, the present invention is described in detail, although thepresent is not limited to these compounds and uses.

EXAMPLE Example 1: Preparation of Dihydroxydiphenyl Nitrileoxide

Preparation of Triisopropylsilyl (TIPS) Benzophenone 1-2Dihydroxybenzophenone 1-1 (17 g, 78 mmol), imidazole (20 g, 300 mmol),and N,N-dimethyl-4-aminopyridine (DMAP: 4.1 g, 32 mmol) were dissolvedin anhydrous tetrahydrofuran (THF: 400 mL), and triisopropylsilylchloride (33 g, 170 mmol) was added at 0° C. Then, the reaction mixturewas stood for 1 day at a room temperature. The solvent was evaporatedunder reduced pressure, and dichloromethane was added. The mixture wasseparated with water, and dried. The solvent was evaporated underreduced pressure, and the residue was purified a silica gel columnchromatography (ethyl acetate:hexane=1:50) to obtain a colorlesstransparent oil (30 g, 60 mmol, 73%).

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.74-7.71 (d, J=8.0 Hz, 4H), 6.94-6.92(d, J=8.0 Hz, 4H), 1.32-1.26 (m, 6H), 1.13-1.11 (d, J=8.0 Hz, 36H) ppm

Preparation of TIPS Diphenylnitroethene 1-4

TIPS benzophenone 1-2 (21 g, 40 mmol) was added to THF (40 mL), andcooled to 0° C. under Ar atmosphere. Lithium bis(trimethylsilyl)amide(48 mL, 48 mmol) was added, and stirred for one day at a roomtemperature. The solvent was evaporated under reduced pressure, andethyl acetate was added. The reaction mixture was separated with water,saturated saline solution. The solvent was evaporated under reducedpressure, and nitromethane (40 mL) was added. The mixture was refluxedat 115° C. for one day. The solvent was distilled off to obtain a brownoil. This compound was purified by a flash column chromatography to anorange oil. This was used in the next reaction.

Preparation of TIPS Diphenyl Nitrileoxide 1-5

The crude TIPSdiphenylnitroethene 1-4 was added to anhydrous THF (400mL), and cooled to −78° C. under Ar atmosphere. n-BuLi (38 mL, 60 mmol)was added, and stirred for 30 minutes. A concentrated sulfuric acid(>95%, 20 mL, 400 mmol) was added, and stirred as 0° C. for 30 minutes.The mixture was separated with water, and dried. The solvent was removedunder a reduced pressure to obtain an orange oil. This was used in thenext reaction.

Preparation of Dihydroxydiphenyl Nitrileoxide 1-6

The crude TIPS diphenyl nitrileoxide 1-5 was dissolved in THF (480 mL),and tetra-n-butylammonium fluoride (TBAF: 73 mL, 73 mmol) was added andstirred for 10 minutes. Dichloromethane was added at an appropriateamount, separated with water and saturated saline solution, and dried.The solvent was evaporated under reduced pressure, and the residue waspurified by a silica gel column chromatography (hexane→hexane:ethylacetate=8:1→4:1→2:1) to obtain a yellow oil (4.1 g, 14 mmol, 34%).

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.05-7.03 (d, J=8.0 Hz, 4H), 6.77-6.75(d, J=8.0 Hz, 4H), 2.28-2.25 (t, J=7.0 Hz, 4H), 1.28 (m, 4H), 0.86-0.83(t, J=7.0 Hz, 3H) ppm

Example 2: Condensation Polymerizing Reaction Using DihydroxydiphenylNitrileoxide

Preparation of PE-CNO-5

Dihydroxydiphenyl nitrileoxide 1-6 (0.15 g, 0.50 mmol) and bisphenol A(0.11 g, 0.50 mmol) was added to dehydrated dichloromethane (1.0 mL),and triethylamine (0.44 mL, 4.0 mmol) was added while stirring at 0° C.Then, a solution which adipoyl chloride (0.18 g, 0.1 mmol) was dissolvedin chloroform (1 mL) was added slowly, and then stirred for 2 hours at aroom temperature. The product was reprecipitated in methanol, and ether.The resulting pale yellow solid was dissolved in chloroform, separatedwith water, and dried. The solvent was evaporated under reduced pressureto obtain a pale yellow solid (200 mg, 47%).

Yield, 39%

Number average molecular weight (GPC), 14,000

M_(w)/M_(n) (GPC), 2.5

Copolymerization Ratio (¹H NMR), 1:1

1H NMR (400 MHz, 298 K, CDCl₃): δ 7.29-7.27 (d, J=8.4 Hz, 4H, Ph-),7.21-7.20 (d, J=8.4 Hz, 4H, Ph-), 7.08-7.06 (d, J=8.4 Hz, 4H, Ph-),6.98-6.96 (d, J=8.4 Hz, 4H, Ph-), 2.61 (m, 8H, —CH₂ CH₂CH₂ CH₂ —), 2.34(m, 2H, —CH₂ CH₂CH₂CH₃), 1.86 (m, 8H, —CH₂ CH₂CH₂ CH₂—), 1.65 (m, 6H,C(CH₃ )₂), 1.34 (m, 4H, —CH₂ CH₂ CH₂CH₃), 0.88 (m, 3H, —CH₂CH₂CH₂ CH₃ )ppm

Preparation of PE-CNO-10

Dihydroxydiphenyl nitrileoxide 1-6 (0.30 g, 1.00 mmol) was added todehydrated dichloromethane (1.0 mL), and triethylamine (0.44 mL, 4.0mmol) was added while stirring at 0° C. Then, a solution which adipoylchloride (0.18 g, 0.1 mmol) was dissolved in chloroform (1 mL) was addedslowly, and then stirred for 2 hours at a room temperature. The productwas reprecipitated in methanol, and ether. The resulting pale yellowsolid was dissolved in chloroform, separated with water, and dried. Thesolvent was evaporated under reduced pressure to obtain a pale yellowsolid (200 mg, 47%).

Yield, 47%

Number average molecular weight (GPC), 15000

M_(w)/M_(n), 3.4

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.30-7.28 (d, J=7.8 Hz, 4H, Ph-),7.09-7.07 (d, J=7.8 Hz, 4H, Ph-), 2.63 (m, 4H, —CH₂ CH₂CH₂ CH₂ —), 2.34(m, 2H, —CH₂ CH₂CH₂CH₃), 1.77 (m, 4H —CH₂ CH₂CH₂ CH₂—), 1.34 (m, 4H,—CH₂ CH₂CH₂ CH₃), 0.89 (m, 3H, —CH₂CH₂CH₂ CH₃ ) ppm

Example 3: Click Reaction of PE-CNO and Allyl Trimethylsilane

Preparation of PE-Isoxazoline-5

PE-CNO-10 (25 mg, 0.057 mmol) and allyl trimethylsilane (65 mg, 0.57mmol) were dissolved in chloroform (0.5 mL), and stirred for 16 hour at40° C. The solvent and unreacted allyl trimethylsilane were evaporatedto obtain a yellow solid.

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.28-7.26 (d, J=7.8 Hz, 4H, Ph-),7.22-7.20 (d, J=7.8 Hz, 4H, Ph-), 7.07-7.05 (d, J=7.8 Hz, 4H, Ph-),6.98-6.96 (d, J=8.4 Hz, 4H, Ph-), 4.58 (m, 1H, —CNOCHCH₂—), 2.63 (m, 8H,—CH₂ CH₂CH₂ CH₂ —), 2.36 (m, 2H, —CH₂ CH₂CH₂CH₃), 2.21 (m, 2H, —CNOCHCH₂—), 1.88 (m, 8H, —CH₂ CH₂CH₂ CH₂—), 1.65 (m, 6H, C(CH₃ )₂), 1.43 (m, 2H,—CH₂ CH₂ CH₂CH₃), 1.08 (m, 4H, —CH₂CH₂CH₂CH₃, —CH₂ Si(CH₃)₃), 0.81 (m,3H, —CH₂CH₂CH₂ CH₃ ), 0 (s, 9H, Si(CH₃ )₃) ppm

Preparation of PE-Isoxazoline-10

PE-CNO-10 (25 mg) and allyl trimethylsilane (65 mg, 0.57 mmol) weredissolved in chloroform (0.5 mL), and stirred for 16 hour at 40° C. Thesolvent and unreacted allyl trimethylsilane were evaporated to obtain apale yellow solid.

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.30-7.28 (d, J=7.8 Hz, 4H, Ph-),7.07-7.05 (d, J=7.8 Hz, 4H, Ph-), 4.59 (m, 1H, —CNOCHCH₂—), 2.65 (m, 4H,—CH₂ CH₂CH₂ CH₂ —), 2.34 (m, 2H, —CH₂ CH₂CH₂CH₃), 2.23 (m, 2H, —CNOCHCH₂—), 1.89 (m, 4H, —CH₂ CH₂CH₂ CH₂—), 1.34 (m, 2H, —CH₂ CH₂ CH₂CH₃), 1.08(m, 4H, —CH₂CH₂ CH₂ CH₃, —CH₂ Si(CH₃)₃), 0.80 (m, 3H, —CH₂CH₂CH₂ CH₃ ),0 (s, 9H, SiCH₃ ) ppm

Example 4: Crosslinking Reaction of Natural Rubber by PE-CNO

Crosslinking Reaction by PE-CNO-5

A natural rubber was dissolve in toluene, and PE-CNO-5 was added andreacted at 90° C. The produced polymer was immersed in chloroform forone day, and dried under air at a room temperature and under vacuum at70° C. to obtain a pale yellow network polymer (53%).

Yield: 53%

Degree of swelling (CHCl₃): 5700

Crosslinking Reaction by PE-CNO-10

A natural rubber (67 mg) was dissolve in toluene (1 mL), PE-CNO-10 (7.0mg) was added and reacted at 90° C. The produced polymer was immersed inchloroform for one day, and dried under air at a room temperature andunder vacuum at 70° C. to obtain a pale yellow network polymer (39 mg,53%).

Yield: 67%

Degree of swelling (CHCl₃): 3700%

Example 5: Preparation of OH Diphenyl Nitrileoxide

Preparation of OH Benzophenone 2-2

4-hydroxy benzophenone (9.9 g, 50 mmol), 2-bromoethanol (7.5 g, 60 mmol)and potassium carbonate (10 g, 75 mmol) were added toN,N-dimethylformamide (DMF, 150 mL), and stirred at 90° C. for one day.A solvent was distilled off, and dichloromethane was added. The mixtureextracted with water and saturated saline solution, and dried. A solventwas distilled off to obtain a pale yellow powder (crude yield 12 g).This compound was used in the next reaction.

Preparation of TIPS benzophenone 2-3 The crude 2-2 (12 g), imidazole(8.5 g, 130 mmol), and DMAP (1.5 g, 1.3 mmol) were dissolved inanhydrous THF (250 mL), and triisopropylsilyl chloride (19 g, 100 mmol)was added at 0° C. The mixture was returned to a room temperature andreacted for one day. The solvent was evaporated under reduced pressure.The dichloromethane was added and separated with water, and dried. Thesolvent was evaporated under reduced pressure. The residue was purifiedby a silica gel column chromatography (ethyl acetate:hexane=1:30) toobtain a pale oil (22 g, 45 mmol, 90%).

Preparation of TIPS Diphenylnitroethene 2-5

TIPS benzophenone 2-3 (11 g, 23 mmol) was added to THF (20 mL), andcooled to 0° C. under Ar atmosphere. Lithium bis(trimethylsilyl)amide(19 mL, 25 mmol) was added, and stirred at a room temperature for oneday. The solvent was evaporated under reduced pressure, and ethylacetate was added. The mixture was separated with water and saturatedsaline solution. The solvent was evaporated under reduced pressure.Nitromethane (25 mL) was added, and refluxed at 115° C. for one day. Asolvent was distilled off to obtain a brown oil. This compound was usedin the next reaction.

Preparation of TIPS Diphenyl Nitrileoxide 2-6

The crude 2-5 (14 g) was added to anhydrous THF (350 mL), and cooled at−78° C. under Ar atmosphere. n-BuLi (25 mL, 64 mmol) was added, andstirred for 30 minutes. A concentrated sulfuric acid (>95%, 17 mL, 320mmol) was added, stirred at 0° C. for 30 minutes. The mixture wasseparated water, and dried. The solvent was evaporated under reducedpressure. The residue was purified by a silica gel column chromatography(dichloromethane:hexane=1:2) to obtain a yellow oil (5.8 g, 12 mmol,54%).

Preparation of OH Diphenyl Nitrileoxide 2-7

TIPS diphenyl nitrileoxide 2-6 (2.0 g, 4.5 mmol) was dissolve in THF (50mL), and TBAF (1.7 mL, 6.7 mmol) was added and stirred for 20 minutes.Dichloromethane was added, and the mixture was separated with water andsaturated saline solution, and dried. The solvent was evaporated underreduced pressure. The residue was purified by a silica gel columnchromatography (dichloromethane:hexane=10:1) to obtain a yellow oil (2.6g, 8.2 mmol, 97%).

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.37-7.28 (m, J=8.7 Hz, 5H), 7.18-7.16(d, J=8.7 Hz, 2H), 6.82-6.80 (d, J=8.7 Hz, 2H), 5.16 (s, 1H), 2.38-2.34(t, J=6.8 Hz, 2H), 1.37 (m, 4H), 0.93-0.89 (t, J=6.8 Hz, 3H) ppm

Example 6: Ring-Opening Polymerization Using OH Diphenyl Nitrileoxide asan Initiator

Preparation of Macromolecular Nitrileoxide PVL-CNO-2

δ-valerolactone (0.96 g, 9.6 mmol) and OHdiphenyl nitrileoxide 3-6 (0.20g, 0.64 mmol) were added to dehydrated toluene (5 mL), and diphenylphosphate (0.16 g, 0.64 mmol) was added while stirring at a roomtemperature, and stirred for 2 hours. Reprecipitation inhexane:ethanol=(9:1) (100 mL) and filtration were repeated two times toobtain a white solid 0.83 g (72%). As a result of the GPC measurement,unimodal peak (Mn=6100, Mw/Mn=1.21) was observed.

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.34-7.26 (m, 5H, Ph-) 7.22-7.20 (d,J=8.0 Hz, 2H, Ph-), 6.88-6.86 (d, J=8.0 Hz, 2H, Ph-), 4.44-4.42 (t,J=4.0 Hz, 2H, —OCH₂CH₂O—), 4.17 (m, 2H, —OCH₂CH₂O—), 4.08 (m, 62H,—CH₂CH₂OCO—) 3.67-3.64 (t, J=6.0, 2H, —CH₂CH₂OH), 2.34 (m, 64H,—OCOCH₂CH₂—, —CH₂CH₂CH₂CH₃), 1.68 (m, 124H, —CH₂CH₂CH₂CH₂—), 1.35 (m,4H, —CH₂CH₂CH₂CH₃), 0.90-0.87 (m, J=6.0, 3H, —CH₂CH₂CH₂CH₃) ppm

Example 7: Click Reaction of PVL-CNO-2 and Allyl Trimethylsilane

Preparation of PVL-Isoxazoline

PVL-CNO-2 (75 mg, 0.022 mmol) and allyl trimethylsilane (25 mg, 0.22mmol) were dissolved in chloroform (0.5 mL), and stirred at 40° C. forone day. The solution was reprecipitated in hexane (50 mL) to obtain awhite solid.

¹H NMR (400 MHz, 298 K, CDCl₃): δ 7.32-7.18 (m, 7H), 6.87-6.85 (d, J=8.0Hz, 2H), 4.59 (m, 1H), 4.45-4.43 (t, J=4.0 Hz, 2H), 4.26 (m, 2H), 4.09(m, 60H) 3.67-3.64 (t, J=6.0, 2H), 2.77-2.71 (m, 1H) 2.40-2.32 (m, 61H),1.69-1.67 (m, 120H), 1.28-1.24 (m, 2H), 1.10-1.08 (m, 3H) 0.85-0.79 (m,4H), 0.00 (s, 9H) ppm

Example 8

Preparation of Nitroalkane 18-3

Sodium hydride (1.5 g) was washed with hexane. After adding an inertgas, dry DMF (40 mL) was added. 1,6-hexanediol (7.1 g) was added at 0°C., and stirred for 1 hour. diphenyl nitroethene (4.5 g) dissolved indry DMF (10 mL) was added, and stirred for 1 hour at a room temperature.A small amount of acetic acid was added at 0° C., dissolved indichloromethane, and then washed with deionized water and saturatedsaline solution. The organic layer was dried over anhydrous sodiumsulfate, and the solvent was distilled off. The residue was purified bya silica gel chromatography (ethyl acetate/hexane=1/1) to obtainNitroalkane 18-3 (5.9 g, yield 86%) as a yellow viscous material.

Preparation of Monomer NAMA

Nitroalkane 18-3 (2.1 g) and pyridine (0.48 g) was dissolved in drydichloromethane (15 mL), and methacylic acid chloride (0.56 g) was addeddropwise at 0° C., and stirred for 1 hour at a room temperature. Afterdissolving in chloroform, the mixture was washed with saturated salinesolution. The organic layer was dried over anhydrous sodium sulfate, andthe solvent was distilled off. The residue was purified by a silica gelchromatography (chloroform/hexane=3/1) to obtain a colorless clearliquid NAMA (1.0 g, yield 42%).

¹H NMR (300 MHz, CDCl₃, ppm) δ 7.67-7.24 (m, 10H, Ph), 6.09 (s, 1H,H₂C═C), 5.43 (s, 1H, H₂C═C), 5.34 (s, 2H, CH₂NO₂), 4.13 (t, 2H, J=6.7Hz, OCH₂), 4.13 (t, 2H, J=6.7 Hz, C═OOCH₂), 3.56 (t, 2H, J=6.2 Hz,OCH₂), 1.94 (s, 1H, C═CCH₃), 1.72-1.60 (m, 4H, OCH₂CH₂), 1.50-1.31 (m,CH₂CH₂)

Preparation of PNAMA by Free Radical Polymerization

[M]/[I]=33, [M]=0.6M wherein M is NAMA, and I is AIBN.

NAMA (0.5 g), azobisisobutyronitrile (AIBN) (6.0 mg), anisole (2.0 mL)was added to a reactor. After freeze-degassing three times, the mixturewas stirred at 90° C. for 4 hours. Reprecipitation in hexane/ethanol=9/1was performed three times to obtain a white solid (0.29 g).

¹H NMR (400 MHz, CDCl₃, ppm): δ 7.3 (m, 10H, Ph-H), 5.3 (s, 2H,—C(Ph)₂-CH₂—NO₂), 3.9 (br, 2H, —C(O)O—CH₂—), 3.4 (br, 2H,—C(Ph)₂-O—CH₂—), 2.1-0.8 (m, 13H, —O—C₄H₈—O—, —CH2-C(CH₃)—C(O)—)

Preparation of PCNOMA

PNAMA (0.18 g), dry dichloromethane 10 mL, p-chlorophenyl isocyanate(0.67 g) and triethylamine (0.68 g) was added under an inert gas, andstirred for 2 hours at a room temperature. The insoluble portion wasfiltered off, and the solvent was evaporated. Reprecipitation inhexane/ethanol=9/1 was performed three times to obtain a white solid (42mg, yield 23%).

¹H NMR (400 MHz, CDCl₃, ppm): δ 7.3 (m, 10H, Ph-H), 3.9 (br, 2H,—C(O)O—CH₂—), 3.4 (br, 2H, —C(Ph)₂-O—CH₂—), 2.1˜0.7 (m, 13H, —O—C₄H₈—O—,—CH2-C(CH3)-C(O)—)

INDUSTRIAL APPLICABILITY

The compound of the present invention can be suitably used in variousapplications, for example, hydrophilizing agent, surface treating agent,polymerization initiator, polymerizable monomer, a crosslinking agent,denaturation treatment agent, thermosetting resin, thermosettingelastomer, liquid rubber, low temperature property rubber, modifier offiller or reactive compatibilizing agent.

1. A compound of the formula (I):

wherein: R¹ is a hydrogen atom or a hydrocarbon group; R² is —R⁴—R⁵; R³is —R⁴—R⁵ or —R⁴—R⁶; R⁴ is a divalent organic group; R⁵ is OH, SH, COOHor NHR⁹; R⁹ is a hydrogen atom or an alkyl group having 1-6 carbonatoms; and R⁶ is a hydrogen atom or an alkyl group having 1-6 carbonatoms.
 2. A compound of the formula (III):

wherein: R²¹ is a hydrogen atom or an alkyl group; R²² is a hydrogenatom or an alkyl group; and R²³ is a divalent organic group.
 3. Acopolymer comprising one or more monomer units of the formula (Ia):

wherein: R¹ is a hydrogen atom or a hydrocarbon group; R^(2′) and R^(3′)are each independently −R⁴—R^(5′)—; R⁴ is a divalent organic group;R^(5′) is each independently —O—, —S—, —CO— or —NR⁹—; and R⁹ is ahydrogen atom or an alkyl group having 1-6 carbon atoms, and one or morecondensation polymerizable or addition polymerizable monomer units.
 4. Apolymer comprising one or more monomer units of the formula (IIa):

wherein: R²¹ is a hydrogen atom or an alkyl group; R²² is a hydrogenatom or an alkyl group; and R²³ is a divalent organic group.
 5. Apolymer comprising one or more monomer units of the formula (IIIa):

wherein: R²¹ is a hydrogen atom or an alkyl group; R²² is a hydrogenatom or an alkyl group; and R²³ is a divalent organic group.
 6. Acomposition applied to a material containing a group reactive with anitrileoxide group, comprising one or more polymers according to claim3.
 7. The composition according to claim 6, which is a crosslinkingagent.
 8. A polymer comprising one or more ring-opening polymerizablemonomer units, having a group of the formula (Ib):

wherein: R¹ is a hydrogen atom or a hydrocarbon group; R^(2′) is—R⁴—R^(5′)—; R³ is —R⁴—R⁶; R⁴ is a divalent organic group; R^(5′) is—O—, —S—, —CO—O— or —NR⁹—; R⁹ is a hydrogen atom or an alkyl grouphaving 1-6 carbon atoms; and R⁶ is a hydrogen atom or an alkyl grouphaving 1-6 carbon atoms, at one terminal of the main chain.
 9. A polymercomprising one or more ring-opening polymerizable monomer units, havinga group of the formula (Ib):

wherein: R¹ is a hydrogen atom or a hydrocarbon group; R^(2′) is—R⁴—R^(5′)—; R³ is —R⁴—R⁶; R⁴ is a divalent organic group; R^(5′) is—O—, —S—, —CO—O— or —NR⁹—; R⁹ is a hydrogen atom or an alkyl grouphaving 1-6 carbon atoms; and R⁶ is a hydrogen atom or an alkyl grouphaving 1-6 carbon atoms, at one terminal of the main chain and anitrileoxide group at the other terminal of the main chain.
 10. Apolymer comprising one or more ring-opening polymerizable monomer units,having one moiety of the formula (Ic):

wherein: R¹ is a hydrogen atom or a hydrocarbon group; R^(2′) and R^(3′)are each independently —R⁴—R^(5′)—; R⁴ is a divalent organic group;R^(5′) is each independently —O—, —S—, —CO— or —NR⁹—; R⁹ is a hydrogenatom or an alkyl group having 1-6 carbon atoms; and R^(2′) and R^(3′)are directly attached to the polymerizable monomer unit, in themolecular main chain.
 11. A composition applied to a material containinga group reactive with a nitrileoxide group, comprising one or morepolymers according to claim
 8. 12. The composition according to claim11, which is a grafting agent.
 13. A composition applied to a materialcontaining a group reactive with a nitrileoxide group, comprising one ormore polymers according to claim
 9. 14. A composition applied to amaterial containing a group reactive with a nitrileoxide group,comprising one or more polymers according to claim
 10. 15. Thecomposition according to claim 13, which is a grafting agent.
 16. Thecomposition according to claim 14, which is a grafting agent.